Si-containing film forming precursors and methods of using the same

ABSTRACT

Methods for producing halosilazane comprise halogenating a hydrosilazane with a halogenating agent to produce the halosilazane, the halosilazane having a formula(SiHa(NR2)bXc)(n+2)Nn(SiH(2−d)Xd)(n−1),wherein each a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1; wherein X is selected from a halogen atom selected from F, Cl, Br or I; each R is selected from H, a C1-C6 linear or branched, saturated or unsaturated hydrocarbyl group, or a silyl group [SiR′3]; further wherein each R′ of the [SiR′3] is independently selected from H, a halogen atom selected from F, Cl, Br or I, a C1-C4 saturated or unsaturated hydrocarbyl group, a C1-C4 saturated or unsaturated alkoxy group, or an amino group [—NR1R2] with each R1 and R2 being further selected from H or a C1-C6 linear or branched, saturated or unsaturated hydrocarbyl group, provided that when c=0, d≠0; or d=0, c≠0.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 16/449,070 filed Jun. 21, 2019, which is a continuation-in-partapplication of U.S. patent application Ser. No. 15/692,544 filed Aug.31, 2017, which is a continuation of Ser. No. 14/738,039 filed Jun. 12,2015, now issued as U.S. Pat. No. 9,777,025, which claims the benefit ofU.S. Provisional Patent Application No. 62/140,248, filed Mar. 30, 2015,all applications being incorporated by reference herein in theirentireties for all purposes.

TECHNICAL FIELD

Disclosed are Si-containing film forming compositions comprisinghalosilazanes or halogenated hydrosilazanes and mono-substitutedtrisilylamine precursors, methods of synthesizing the same, and methodsof using the same to deposit Si-containing films using vapor depositionprocesses for manufacturing semiconductors, photovoltaics, LCD-TFT, flatpanel-type devices, refractory materials, or aeronautics.

BACKGROUND

A variety of silicon containing precursor have been used to depositSi-containing thin films on various substrates by vapor depositionprocesses. The choice of the suitable silicon precursor and, whenapplicable, of the co-reactant are generally driven by the target filmcomposition and properties, as well as by the constraints brought by thesubstrate on which the film is to be deposited. Some substrates mayrequire low temperature deposition processes.

For instance, deposition on plastic substrates or Si substrates coatedwith organic films may require deposition temperatures below 100° C.(i.e., 20° C.-100° C.), while maintaining a reasonable deposition rateto be of industrial interest. Such films may be used as spacer-definedlithography application in semiconductor fabrication, but also forsealing organic light-emitting diode (OLED) devices or creating moisturediffusion barriers on films. Similar constraints at differenttemperature ranges appear in the different steps of semiconductormanufacturing, such as, capping layers over metals, gate spacers, etc.

Trisilylamine (TSA) is a molecule with a high Si content and has theformula of N(SiH₃)₃. TSA may be used as a low temperature (T) siliconnitride precursor (see, e.g., U.S. Pat. No. 7,192,626), as well as aprecursor for flowable CVD (see, e.g., U.S. Pat. No. 8,846,536, US2014/0057458 or U.S. Pat. No. 8,318,584). However, while TSA appears asa versatile precursor (Carbon-free and low T capability) for a varietyof thin film deposition processes, it's applicability to thermal ALD hasbeen limited (see, e.g., U.S. Pat. No. 8,173,554, indicating that plasmaactivation is necessary to obtain a meaningful growth per cycle).

US2014/0363985 A1 discloses amino-silylamines used for forming asilicon-containing thin-film having a generic formula ofR¹R²R³Si—N(SiR⁴R⁵—NR⁶R⁷)₂, wherein R¹ to R⁵ are each independentlyhydrogen, halogen, (C1-C7)alkyl, (C2-C7)alkenyl, (C2-C7)alkynyl,(C3-C7)cycloalkyl or (C6-C12)aryl. US2014/0158580A describes analkoxysilylamine having a TSA-like structure. U.S. Pat. No. 7,122,222uses a Si—C bond free hydrazinosilane precursor [R¹₂N—NH]_(n)Si(R²)_(4−n)] to depict SiN, SiO₂ and SiON films. Silazanecompounds N—(SiR¹R²R³)_(m)R⁴ _(3−m) disclosed in WO2013/058061 are usedas a coating gas. (RR¹R²M^(a))_(y)A(R³)_(x) disclosed in U.S. Pat. No.5,332,853 is used as a catalytic compound to produce a functionalizedalkylalkali metal compound. Similar patents include U.S. Pat. Nos.5,663,398A, 5,332,853A, 5,340,507A, EP 525881 A1, etc.

Methods for preparation of inorganic halogenated silazanes orhalosilazane have been experimentally demonstrated but are limited invarious ways.

Marcus et al. (“Formation of fluorosilylamines by the interaction oftrisilylamine with phosphorus pentafluoride. Synthesis of1,1′-difluorotrisilylamine”, Inorg. Chem. (1975), 14(12), 3124-5)disclosed TSA-F_(x) (x=1-3) which were prepared non-selectively from TSAand PF₅ between −50° C. and 0° C. The reaction is(SiH₃)₃N+PF₅=(SiH_(3−x)F_(x))₃N+[HPF₄] (x=1-3),which produced a polymeric solid and mixture of fluorinated compounds.Mono- and trifluorinated compounds were not isolated in pure form butwere observed only on chromatogram, while difluorinated compound(SiH₃)N(SiH₂F)₂ was isolated by fractional distillation in a pure form.The yield of fluorosilylamines produced in the reactions did not exceed5-10% overall.

Cradock et al. (“Reactions of Tin(iv) Chloride with Silyl Compounds.Part 1. Reactions with Inorganic Silyl Compounds”, Stephen Cradock, E.A. V. Ebsworth, and Narayan Hosmane, Dalt. Trans.: Inorg. Chem. (1975)p. 1624-8) disclosed TSA-Cl_(x) (x=1-3) compounds that were preparedfrom SnCl₄ and TSA:(SiH₃)₃N+SnCl₄=(SiH_(3−x)Cl_(x))₃N+SnCl₂+HCl (x=1-3).

However, as the HCl byproduct cleaved Si—N bonds, the reaction sufferedfrom the lack of selectivity and the major product was found to be MCS.The yields of mono-, bis- and tris-chlorinated TSA were 20, 15 and 10%,respectively.

Bacqué et al. (“Synthesis and chemical properties of1,3-dichloro-1,3-dihydridodisilazanes”, Eric Bacqué, Jean-Paul Pillot,M. Birot, J. Dunogués, M. Pétraud, J. Organomet. Chem. V.481, 2, 15 Nov.1994, p. 167-172) disclosed a method for preparation of chlorinatedaminosilanes and silazanes by displacement reactions by chlorosilanes:R¹SiHCl₂+(Me₃Si)₂N—R²=(R¹SiHCl)(Me₃Si)N—R²+Me₃SiCl, and2R¹SiHCl₂+(Me₃Si)₂N—R²=(R¹SiHCl)₂N—R²+2Me₃SiCl(R¹=Me, Et, Ph, R²=H, Me) catalyzed by [^(n)Bu₄N]F. Silbiger et al.(“The Preparation of Chlorodisilazanes and Some of Their Derivatives”,J. Silbiger, and J. Fuchs, Inorg. Chem., 1965, 4 (9), pp 1371-1372)disclosed a method for preparation of the same molecules as Bacqué etal. synthesized but catalyzed by AlCl₃. Compounds (R¹SiHCl)(Me₃Si)N—R²and (R¹SiHCl)₂N—R² having only Si—C and Si—Cl bonds are thermallystable, according to Silbiger et al., while those possessing both Si—Hand Si—Cl bonds slowly decompose after several days at room temperature,under inert gas producing NH₄Cl, oligomers, and MeHSiCl₂, according toBacqué et al. While the given method is widely applied for preparationof organic aminosilanes, only one example reported for the carbon freehomologue (SiH₂Cl)₂NH, that is,2SiH₂Cl₂+(Me₃Si)₂NH=(SiH₂Cl)₂NH+2Me₃SiCl.

Reaction proceeded in the presence of AlCl₃ catalyst and was used forsynthesis of aminosilanes (SiH₂NR₂)₂NH according to Gi et al. toWO2018182305 A1. However, no evidence was provided for the (SiH₂Cl)₂NHand the proton resonance of N—H group as well as FT-IR evidence of N—Hwas not provided for any aminosilane (SiH₂NR₂)₂NH prepared from(SiH₂Cl)₂NH by aminolysis reaction as disclosed in patent. The reactionapparently has low selectivity as the reported yield ofbis(ethylmethylaminosilyl)amine prepared from (SiH₂Cl)₂NH intermediateis 33%. In addition, according to WO 2015135698 to Hoppe et al.,disilylamine (SiH₃)₂NH is reported to be unstable itself, producing TSAand ammonia or reactive toward the SiH₃Cl used in the synthesis above.

U.S. Pat. No. 9,777,025 B2 to Girard et al. disclosed preparation ofmonohalogenated TSA derivatives. The invention proposes that halogenatedaminosilanes TSA-Hal (Hal=Cl, Br, I) might be synthesized from mixtureof dihalosilane SIH₂X₂ with monohalosilane SiH₃X (wherein X is Cl, Br,or I) and NH₃ in a flow-through tubular reactor. However neitherexamples of the synthesis for production of TSA-Hal nor any optimizationof conditions were provided in the given patent precluding any judgementabout yield and selectivity of process. The proposed method might afforda high amount of side products because all earlier references, forexample, Stock et al. (“Siliconhydrides X. Nitrogen-containingcompounds”. Stock, Alfred; Somieski, Karl; Ber, B: Abhandlungen (1921),54B, 740-58), Zhang et al. to CN 102173398 A, JP1917728 C3 to Matsumotoet al., JP1777774 C3 to Matsumoto et al., JP3516815 B2 to Nakajima etal., U.S. Pat. No. 4,397,828 A to Seyferth et al., WO 9119688 A1 toDelaet, state that interaction of SiH₂X₂ and ammonia produces a solidchlorine free polymer and proceeds according to the reaction:3NH₃+H₂SiCl₂→2NH₄Cl+[SiH₂(NH)]_(x).

US 2013/0209343 A1 to Korolev discloses that higher puritymonochlorosilane produces larger quantities of TSA by reaction ofmonochlorosilane and ammonia and application of impure SiH₃Cl leads toformation of mixture containing TSA-Cl, TSA-Cl₂ and TSA-oligomers, butwhat impurity triggers formation of chlorinated compounds was notreported.

Gamboa (“Chlorinated and nitrogenated derivatives of the silanes”,Anales de la Real Sociedad Espanola de Fisica y Quimica, Serie B:Quimica (1950), 46B, 699-714) attempted to prepare (SiH₃SiH₂)₃N byreaction of monochlorinated (SiH₃SiH₂Cl) and dichlorinated (Si₂H₄Cl₂)disilane and ammonia (NH₃). The reaction produced large amounts ofpolymeric material contaminated with NH₄Cl from which the desired amine(SiH₃SiH₂)₃N or any isolable low molecular weight compound was notrecovered.

Pflugmacher et al. (“Formation of silicon-nitrogen compounds in the glowdischarge. I.”, Zeitschrift fuer Anorganische und Allgemeine Chemie(1957), 290, 184-90) disclosed the fully chlorinated homologue (Cl₃Si)₃Nis a volatile solid and can be obtained by reacting a SiCl₄ and N₂ in aglow discharge tube. Alternatively, Anon (IP.com Journal (2013), 13 (1B), 8, IP.COM DISCLOSURE NUMBER: IPCOM000224804D) proposed to synthesize(Cl₃Si)₃N directly from tetrachlorosilane and ammonia. However, A. Stock(Hydrides of Boron and Silicon, Cornell University Press, Ithaca, N.Y.,1933) and Richetto et al. (“Qualitative analysis of silicon nitridesynthesized by ammonolysis of silicon tetrachloride”, Richetto, K. C.S.; Silva, C. R. M.; Baldacin, S. A., Materials Science Forum (2003),416-418 (Advanced Powder Technology III), 688-692) stated thatinteraction of SiCl₄ and ammonia produces only polymeric solids.

All these disclosures notwithstanding, halogenated aminosilanes are notprepared and utilized commercially at the time.

Catalysts have been apply to the halogenated aminosilanes to try toincrease yields. Organic silanes were chlorinated with variouschlorocarbons in presence of applying highly acidic catalysts such asHCl, B(C₆F₅)₃, AlCl₃, (refer to J. Am. Chem. Soc., 1963, 85 (16), pp2430-2433; J. Am. Chem. Soc., 1969, vol. 91, p. 7076; Appl. Organometal.Chem., 2018; 32: e4442). These substrates are known to cleave Si—N bondor triggering disilylative coupling of carbon free hydrosilazanes suchas TSA (see U.S. Pat. Appl. Publ. (2018), US 20180072571).

One example of catalysis by Palladium on carbon was reported to promotechlorination of ^(i)Pr₃SiH by C₂Cl₆ as disclosed by Pongkittiphan et al.(“Hexachloroethane: a Highly Efficient Reagent for the Synthesis ofChlorosilanes from Hydrosilanes”; Veerachai Pongkittiphan, Emmanuel A.Theodorakis, Warinthom Chavasiri; Tetrahedron Letters (2009), 50(36),5080-5082). Comparative examples below for TSA chlorination with C₂Cl₆and Pd/C reveal that this method is not applicable for hydrosilazanesdisclosed herein; the yield of halosilazanes is below 5% in allcomparative examples.

Yang et al., (“Reduction of Alkyl Halides by Triethylsilane Based on aCationic Iridium Bis(phosphinite) Pincer Catalyst”; Scope, Selectivityand Mechanism; by Jian Yang and Maurice Brookhart; from Adv. Synth.Catal., 2009, 351, p. 175-187) and (“Iridium-Catalyzed Reduction ofAlkyl Halides by Triethylsilane”, by Yang, Jian; Brookhart, Maurice,from Journal of the American Chemical Society (2007), 129(42),12656-12657) and Stöhr et al. (“C—Cl/Si—H Exchange catalysed byP,N-chelated Pt(II) complexes”, by Frank Stöhr, Dietmar Sturmayr, UlrichSchubert, from Chem. Commun., 2002, 2222-2223) report application ofcationic iridium hydride complexes and P,N-chelated Pt(II) complexes forchlorination of organic silanes by chlorocarbons. Cationic complexes maytrigger the polymerization of inorganic silazanes. In addition, allthese complexes of noble metals are made by multi-step synthesis and notavailable commercially, thus precluding their utilization in anindustrial scale process.

In(OAc)₃ and other Indium complexes with related ligands disclosed byMiura et al. (“Indium-Catalyzed Radical Reductions of Organic Halideswith Hydrosilanes”, by Katsukiyo Miura, Mitsuru Tomita, Yusuke Yamada,Akira Hosomi; from J. Org. Chem., 2007, 72 (3), pp 787-792) performed acatalyzed reaction of bromo- and iodoalkanes with PhSiH₃ in THF at 70°C. to produce dehalogenated alkanes, while halogenated silane was notisolated from the reported reaction, precluding any judgement about theyield and selectivity of reaction.

Stock (“Hydrides of Boron and Silicon” by A. Stock, Cornell UniversityPress, Ithaca, N.Y., 1933) discloses Halogens Hal₂ would violentlyoxidize inorganic hydrosilazanes with formation of H-Hal that alsocleaves Si—N bond. Stock also discloses H-Hal itself or in presence ofcatalysts (“Hydrides of Boron and Silicon”, by A. Stock, CornellUniversity Press, Ithaca, N.Y., 1933) would cleave Si—N bonds ofhydrosilazanes.

Transition metal halogenides SnCl₄, CuCl₂, HgBr₂, PdCl₂ etc. (e.g.,Dalt. Trans.; Inorg. Chem. (1975), p. 1624-8; Journal of organometallicchemistry, 2003, vol. 686, p. 3; J. Am. Chem. Soc., v.80 (1958), p.5083) would lead to Si—N bond cleavage and/or formation of polymericproducts.

Halogenides of P, As, B, S and other non-metals disclosed by Cradock etal. (“Reactions of Tin(iv) Chloride with Silyl Compounds. Part 1.Reactions with Inorganic Silyl Compounds”; Stephen Cradock, E. A. V.Ebsworth, and Narayan Hosmane; Journal of the Chemical Society, DaltonTransactions: Inorganic Chemistry (1975), p. 1624-8), Kunai et al.(“Selective synthesis of halosilanes from hydrosilanes and utilizationfor organic synthesis”, A Kunai, J Ohshita, Journal of organometallicchemistry, 2003, vol. 686, 3) and Herbert et al. (“Reactions ofTriethylsilane and Diethylsilane with Inorganic Halides and Acids”;Herbert H. Anderson; J. Am. Chem. Soc., 1958, vol. 80, p. 5083) causecleavage of S—N bonds in aminosilanes and disilazanes as stated in theprior art and shown in the comparative examples.

“Hydrogen-Halogen” redistribution between various Si compounds in thepresence of Lewis acid/base catalysts is disclosed by Moedritzer et al.(“The Redistribution Equilibria of Silanic Hydrogen with Chlorine onMethylsilicon Moieties”, K. Moedritzer, J. Van Wazer, J. Organomet.Chem., v.12 (1968), p. 69-77) and by Whitmore (“Hydrogen-HalogenExchange Reactions of Triethylsilane. A New Rearrangement of NeopentylChloride”, F. C. Whitmore, E. W. Pietrusza, and L. H. Sommer, J. Am.Chem. Soc., 1947, vol. 69, p. 2108). These catalysts would triggerdesilylative coupling as shown in the comparative examples.

Industries using vapor-based deposition processes such as CVD or ALD (inall possible meanings, such as LPCVD, SACVD, PECVD, PEALD, etc.) arestill looking for precursors that are ideal for their applications, i.e.having the highest possible deposition rates within the constraints oftheir processes, substrates and film targets. As such, there is a demandto discover a simple, selective and economical process for preparing ofhalogenated derivatives of silicon-nitrogen compounds, such astrisilylamine, that offers advantages both in terms of economics andcommercial use.

SUMMARY

Disclosed are Si-containing film forming compositions comprising ahalosilazane precursor having a formula:(SiH_(a)(NR₂)_(b)X_(c))_((n+2))N_(n)(SiH_((2−d))X_(d))_((n−1))  (I)where X is selected from a halogen atom selected from F, Cl, Br or I; Reach is selected from H, a C₁-C₆ linear or branched, saturated orunsaturated hydrocarbyl group, or a silyl group [SiR′₃]; and each a, b,c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1. In the subgenuscomprising a silyl group [SiR′₃], each R′ is independently selected fromH, a halogen atom selected from F, Cl, Br or I, a C₁-C₄ saturated orunsaturated hydrocarbyl group, a C₁-C₄ saturated or unsaturated alkoxygroup, or an amino group [—NR¹R²] with each R¹ and R² being furtherselected from H or a C₁-C₆ linear or branched, saturated or unsaturatedhydrocarbyl group. Also disclosed are Si-containing film formingcompositions comprising a mono-substituted TSA precursor having theformula (SiH₃)₂NSiH₂—X, wherein X is a halogen atom selected from Cl, Bror I; an isocyanato group [—NCO]; an amino group [—NR¹R²]; aN-containing C₄-C₁₀ saturated or unsaturated heterocyle; or an alkoxygroup [—O—R]; R¹, R² and R is selected from H; a silyl group [—SiR′₃];or a C₁-C₆ linear or saturated branched, or unsaturated hydrocarbylgroup; with each R′ being independently selected from H; a halogen atomselected from C, Br, or I; a C₁-C₄ saturated or unsaturated hydrocarbylgroup; a C₁-C₄ saturated or unsaturated alkoxy group; or an amino group[—NR³R⁴] with each R³ and R⁴ being independently selected from H and aC₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl group,provided that if R¹=H, then R²≠H, Me or Et. The disclosed Si-containingfilm forming compositions may include one or more of the followingaspects:

-   -   the mono-substituted TSA precursor wherein X is a halogen atom;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—Cl;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—Br;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—I;    -   the mono-substituted TSA precursor wherein X is a isocyanate        —NCO (i.e., being (SiH₃)₂N—SiH₂—NCO);    -   the mono-substituted TSA precursor wherein X is an amino group        [—NR¹R²];    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NiPr₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NHiPr;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NHtBu;    -   the mono-substituted TSA precursor not being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHEt)) (i.e., when X=NR¹R² and R¹ is        SiH₃ and R² is NHEt);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NEt₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NEtMe;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NMe₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NMeiPr;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NEtiPr;    -   the mono-substituted TSA precursor wherein X is —N(SiR₃)₂,        wherein each R is independently selected from a halogen, H, or a        C₁-C₄ alkyl group;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiCl₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiBr₃)₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—N(SiI₃)₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—N(SiH₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂Cl);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NEt₂);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NiPr₂);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHtBu);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂OEt);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂OiPr);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiMe₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—NH(SiMe₃);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiEt₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂Et)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂iPr)₂,    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂nPr)₂;    -   the mono-substituted TSA precursor wherein X is a N-containing        C₄-C₁₀ heterocycle;    -   the mono-substituted TSA precursor wherein the N-containing        C₄-C₁₀ heterocycle is selected from pyrrolidine, pyrrole, and        piperidine;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(pyrrolidine);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(pyrrole);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(piperidine);    -   the mono-substituted TSA precursor wherein X is an alkoxy group        [—O—R];    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OH);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OMe);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OEt),    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OiPr);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OnPr);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OtBu);    -   the mono-substituted TSA precursor wherein X is —O—SiR₃ and each        R is independently selected from H, a halogen, or a C₁-C₄        hydrocarbyl group;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiH₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiCl₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiBr₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSil₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiMe₃);    -   R being an alkyl group selected from Me, Et, Pr, ^(i)Pr, Bu,        ^(i)Bu, or ^(t)Bu;    -   X being selected from a halogen atom selected from F, Cl, Br, or        I;    -   the halosilazane or halogenated hydrosiiazane precursor being        selected from (H₃Si)₂N(SiH₂Cl), (H₃Si)₂N(SiH₂Br),        (H₃Si)N(SiH₂Br)₂, (H₃Si)₂N(SiH₂l), (H₃Si)N(SiH₂Cl)₂,        (H₃Si)(H₂SiCl)N(SiH₂(N_(i)Pr₂)), (H₃Si)(H₂SiBr)N(SiH₂(N₁Pr₂)).        (H₃Si)(H₂SiI)N(SiH₂(N_(i)Pr₂)), (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)),        (H₃Si)(H₂SiBr)N(SiH₂(NEt₂)), (H₃Si)(H₂SiI)N(SiH₂(NEt₂)),        (H₂SiCl)₂N(SiH₂(N_(i)Pr₂)). (H₃SiCl)N(SiH₂(N₁Pr₂))₂,        (H₂SiCl)N(SiH₂(NEt₂))₂;    -   the halosilazane or halogenated hydrosilazane precursor being        selected from (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Cl),        (H₃Si)₂N(SIH₂)N(SiH₃)(SiH₂Br), (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂l);    -   the halosilazane or halogenated hydrosilazane precursor is        (H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂));    -   the halosilazane or halogenated hydrosilazane precursor is        (H₂SiCl)₂N(SiH₂(N^(i)Pr₂));    -   the halosilazane or halogenated hydrosilazane precursor is        (H₂SiCl)₂N(SiH₂(N^(i)Pr₂));    -   the halosilazane or halogenated hydrosilazane precursor is        (H₃Si)(H₂SiCl)N(SiH₂(NEt₂));    -   the halosilazane or halogenated hydrosiiazane precursor is        (H₂SiCl)N(SiH₂(NEt₂))₂;    -   the halosilazanes being produced by halogenation of        (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1))        wherein n≥1, each a, b is independently 0 to 3, a+b=3, R each is        selected from H, a C₁-C₆ linear or branched, saturated or        unsaturated hydrocarbyl group, or a silyl group [SiR′₃]. For the        subgenus comprising a silyl group [SiR′₃] each R′ is        independently selected from H, a halogen atom selected from F,        Cl, Br or I, a C₁-C₄ saturated or unsaturated hydrocarbyl group,        a C₁-C₄ saturated or unsaturated alkoxy group, or an amino group        [—NR¹R²] with each R¹ and R² further being selected from H or a        C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl        group;    -   the halosilazanes being produced by selective halogenation of        (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1))        wherein n≥1, each a, b is independently 0 to 3, a+b=3, R each is        selected from H, a C₁-C₆ linear or branched, saturated or        unsaturated hydrocarbyl group, or a silyl group [SiR′₃]. For the        subgenus comprising a silyl group [SiR′₃] each R¹ is        independently selected from H, a halogen atom selected from F,        Cl, Br or I, a C₁-C₄ saturated or unsaturated hydrocarbyl group,        a C₁-C₄ saturated or unsaturated alkoxy group, or an amino group        [—NR¹R²] with each R¹ and R² further being selected from H or a        C₁-C₆ linear or branched, saturated or unsaturated hydrocarbyl        group;    -   when R is H, the halosilazanes precursors being carbon-free        halosilazanes precursors have a formula        (Si_(a)H_(2a+1))_(n+2−c)(Si_(a)H_(2a+1−m)X_(m))_(c)N_(n)(SiH₂)_((n−1−d))(SiH_(2−b)X_(b))_(d),        where X is selected from a halogen atom selected from F, Cl, Br        or I; a, n≥1, 0<m<2a+1 and b=0-2, 0<c<n+2 and 0≤d<n−1;    -   the carbon-free halosilazanes being produced by halogenation of        hydrosilanes having a general formula        (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)), where a, n≥1;    -   the carbon-free halosilazanes being produced by selective        halogenation of hydrosilanes having a general formula        (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)), where a, n≥1;    -   the Si-containing film forming composition comprising between        approximately 95% w/w and approximately 100% w/w of the        precursor;    -   the Si-containing film forming composition comprising between        approximately 5% w/w and approximately 50% w/w of the precursor;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Al;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw As;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ba;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Be;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Bi;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Cd;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ca;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Cr;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Co;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Cu;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ga;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ge;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Hf;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Zr;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw In;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Fe;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Pb;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Li;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Mg;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Mn;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw W;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ni;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw K;    -   the o Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Na;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Sr;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Th;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Sn;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Ti;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw U;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw V;    -   the Si-containing film forming composition comprising between        approximately 0 ppbw and approximately 500 ppbw Zn;    -   the Si-containing film forming organosilane composition        comprising between approximately 0 ppmw and approximately 500        ppmw Cl;    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and approximately 500 ppmw Br;    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and approximately 500 ppmw I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w TSA;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w (SiH₃)₂—N—SiH₂X, wherein X        is Cl, Br, or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w (SiH₃)₂—N—SiHX₂, wherein X        is Cl, Br, or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w SiH₄;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w SiH₃X, wherein X is Cl, Br,        or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w SiH₂X₂, wherein X is Cl, Br,        or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w SnX₂, wherein X is Cl, Br,        or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w SnX₄, wherein X is Cl, Br,        or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/to HX, wherein X is Cl, Br, or        I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w NH₃;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w NH₄X, wherein X is Cl, Br,        or I;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w ROH, wherein R is C1-C4        alkyl group;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w NH₂R, wherein R is a C1-C4        alkyl group;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w NR₂H, wherein R is a C1-C4        alkyl group;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w HN═R, wherein R is a C1-C4        alkyl group;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w tetrahydrofuran (THF);    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w ether;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w pentane;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w cyclohexane;    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w heptane; or    -   the Si-containing film forming composition comprising between        approximately 0.0% w/w and 0.1% w/w toluene.

Also disclosed are methods of depositing a Si-containing layer on asubstrate. The composition disclosed above is introduced into a reactorhaving a substrate disposed therein. At least part of themono-substituted TSA precursor is deposited onto the substrate to formthe Si-containing layer using a vapor deposition method. Also disclosedare methods for forming a Si-containing film, the method comprising thesteps of introducing into a reactor containing a substrate a vaporincluding a halosilazane or halogenated hydrosilazane precursor having aformula(SiH_(a)(NR₂)_(b)X_(c))_((n+2))N_(n)(SiH_((2−d))X_(d))_((n−1))where X is selected from a halogen atom selected from F, Cl, Br or I; Reach is selected from H, a C₁-C₆ linear or branched, saturated orunsaturated hydrocarbyl group, or a silyl group [SiR′₃]. For thesubgenus comprising a silyl group [SiR′₃] each R′ is independentlyselected from H, a halogen atom selected from F, Cl, Br or I, a C₁-C₄saturated or unsaturated hydrocarbyl group, a C₁-C₄ saturated orunsaturated alkoxy group, or an amino group [—NR¹R²] with each R¹ and R²being further selected from H or a C₁-C₆ linear or branched, saturatedor unsaturated hydrocarbyl group; each a, b, c is independently 0 to 3;a+b+c=3; d is 0 to 2 and n≥1, and depositing at least part of thehalosilazane or halogenated hydrosilazane precursor onto the substrateto form the silicon-containing film on the substrate using a vapordeposition process. The disclosed methods may have one or more of thefollowing aspects;

-   -   introducing into the reactor a vapor comprising a second        precursor;    -   an element of the second precursor being selected from the group        consisting of group 2, group 13, group 14, transition metal,        lanthanides, and combinations thereof;    -   the element of the second precursor being selected from As, B,        P, Si, Ge, Al, Zr, Hf, Ti, Nb, Ta, or lanthanides;    -   the element of the second precursor being selected from the        group consisting of Ti, Hf, Zr, Ta, Nb, V, Al, Sr, Y, Ba, Ca,        As, B, P, Sb, Bi, Sn, Ge, and combinations thereof;    -   introducing a reactant into the reactor,    -   the reactant being selected from the group consisting of O₂, O₃,        H₂O, H₂O₂, NO, NO₂, N₂O, alcohols, diols, carboxylic acids,        ketones, ethers, O atoms, O radicals, O ions, ammonia, N₂, N        atoms, N radicals, N ions, saturated or unsaturated hydrazine,        amines, diamines, ethanolamine, H₂, H atoms, H radicals, H ions,        and combinations thereof;    -   the reactant being selected from the group consisting of O₂, O₃,        H₂O, H₂O₂, NO, NO₂, a carboxylic acid, an alcohol, a diol,        radicals thereof, and combinations thereof;    -   the reactant being plasma treated oxygen;    -   the Si-containing layer being a silicon oxide containing layer;    -   the reactant being selected from the group consisting of N₂, H₂,        NH₃, hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic        amines (such as NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃,        (SiMe₃)₂NH), pyrazoline, pyridine, diamines (such as ethylene        diamine), radical species thereof, and mixtures thereof;    -   the vapor deposition method being a chemical vapor deposition        process;    -   the vapor deposition method being an ALD process;    -   the vapor deposition method being a spatial ALD process;    -   the vapor deposition process being a flowable CVD process;    -   the silicon-containing layer being Si;    -   the silicon-containing layer being SiO₂;    -   the silicon-containing layer being SiN;    -   the silicon-containing layer being SiON;    -   the silicon-containing layer being SiOC;    -   the silicon-containing layer being SiOCN;    -   the silicon-containing layer being SiCN;    -   thermal annealing the Si-containing layer;    -   thermal annealing the Si-containing layer under a reactive        atmosphere;    -   UV curing the Si-containing layer; and    -   Electron beam curing the Si-containing layer.

Also disclosed are methods for halogenation of a hydrosilazane toproduce a halosilazane, the methods comprising the step of contactingthe hydrosilazane with a halogenating agent in a liquid phase to producethe halosilazane, the halosilazane having a formula(SiH_(a)(NR₂)_(b)X_(c))_((n+2))N_(n)(SiH_((2−d))X_(d))_((n−1)),where X is selected from a halogen atom selected from F, Cl, Br or I; Reach is selected from H, a C₁-C₆ linear or branched, saturated orunsaturated hydrocarbyl group, or a silyl group [SiR′₃]; and each a, b,c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1. For thesubgenus comprising a silyl group [SiR′₃] each R′ is independentlyselected from H, a halogen atom selected from F, Cl, Br or I, a C₁-C₄saturated or unsaturated hydrocarbyl group, a C₁-C₄ saturated orunsaturated alkoxy group, or an amino group [—NR¹R²] with each R¹ and R²further being selected from H or a C₁-C₆ linear or branched, saturatedor unsaturated hydrocarbyl group. The disclosed methods may have one ormore of the following aspects:

-   -   adding the halogenating agent into a solvent to form a solution        of the halogenating agent;    -   mixing the solution of the halogenating agent with the        hydrosilazane to form a mixture;    -   separating the halosilazane from the mixture;    -   adding a catalyst to the solution of the halogenation agent;    -   stirring the mixture while monitoring the halogenation;    -   the catalyst being a homogeneous catalyst;    -   the homogeneous catalyst being selected from BPh₃, B(SiMe₃)₃ or        the like;    -   the catalyst being a heterogeneous catalyst;    -   the heterogeneous catalyst being selected from Ru, Pt or Pd in        elemental form;    -   the heterogeneous catalyst being selected from Ru, Pt or Pd        deposited on an inert surface;    -   the inert surface being a surface of carbon, silica, alumina,        molecular sieves, or the like;    -   the catalyst not possessing strong electro- or nucleophilicity;    -   the catalyst not forming acids as strong electro- or        nucleophilic byproducts by interaction with hydrosilazanes;    -   the catalysts being thermally stable;    -   the catalyst accelerating the halogenation reactions in        hydrocarbon solvents such as toluene, xylene or the like;    -   the halogenation agent being a trityl halide selected from Ph₃CX        (X=Cl, Br, I);    -   a selection of the halogenation reagents, catalysts, ratio of        starting compounds and the reaction conditions (e.g., type of        solvents, concentrations, temperature, pressure) for achieving        the best selectivity of halogenation of hydrosilazanes being        highly preferred;    -   the ratio of the amount of the halogenated agent relative to the        hydrosilazane being from approximately 1 to 100% for selective        synthesis of the halosilazane;    -   the ratio of the amount of the halogenated agent relative to the        hydrosilazane being from approximately 20% to approximately 40%        for selective synthesis of the halosilazane;    -   the ratio of the amount of the halogenated agent relative to the        hydrosilazane being from approximately 1 to 100% for selective        synthesis of mono-halogenated Compound        (Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   the ratio of the amount of the halogenated agent relative to the        hydrosilazane being from approximately 20% to approximately 40%        for selective synthesis of mono-halogenated compound        (Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   the ratio of the amount of a trityl halides relative to        (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) being from        approximately 1 to 100% for selective preparation of        monohalogenated compound        (Si_(a)H_(2a)H)_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   the ratio of the amount of trityl halides relative to        (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) being from        approximately 20% to approximately 40% for selective preparation        of monohalogenated compound        (Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   approximately 1.5 to approximately 10 molar excess of        hydrosilazanes relative to the halogenated agent for selective        preparation of monohalogenated compounds        (Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   approximately 1.5 to approximately 10 molar excess of        hydrosilazanes relative to trityl halides for selective        preparation of monohalogenated compounds        (Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or        (SiH_(a)(NR₂)_(b)(X))_((n+2))N_(n)(SiH₂)_((n−1)) (X, R, a, b and        n refer to formula I to IV);    -   the approximate amount of catalyst varying from approximately        0.1 mol % to approximately 10 mol % relative to the halogenating        agent;    -   the approximate amount of catalyst varying from 2 mol % to 6 mol        % relative to the halogenating agent;    -   the selectivity of halogenation of the hydrosilazane ranging        from approximately 30% to approximately 100%;    -   the selectivity of halogenation of the hydrosilazane ranging        from approximately 70% to approximately 97%;    -   the selectivity of halogenation of the hydrosilazane ranging        from approximately 80% to approximately 91%;    -   the yield of halogenation of the hydrosilazane ranging from        approximately 30% to approximately 100%;    -   the yield of halogenation of the hydrosilazane ranging from        approximately 30% to approximately 90%;    -   the yield of halogenation of the hydrosilazane ranging from        approximately 40% to approximately 80%;    -   the yield of halogenation of the hydrosilazane ranging from        approximately 50% to approximately 80%;    -   the yield of halogenation of the hydrosilazane ranging from        approximately 60% to approximately 80%;    -   the solvents being a hydrocarbon solvent;    -   the hydrocarbon solvents being selected from toluene, xylene,        mesitylene, anisole, pentane, hexane, heptane, octane) and        mixtures thereof;    -   the solvents being a halogen-containing hydrocarbon solvent;    -   the halogen-containing hydrocarbon solvents being selected from        methylene chloride, chloroform, chloroethanes, chlorobenzenes or        mixtures thereof;    -   the trityl halides being reacted in a halogenated aliphatic or        aromatic solvent;    -   the halogenated aliphatic or aromatic hydrocarbons including        methylene chloride, chloroform, chloroethanes, chlorobenzenes;    -   the halogenated aliphatic or aromatic hydrocarbons being        recycled and reused;    -   applying trityl halides when a reaction is performed in a        non-halogenated aliphatic or aromatic solvent C_(x)H_(y);    -   the halogenation reaction being performed in a temperature range        from approximately 20° C. to approximately 200° C.;    -   the halogenation reaction being performed in a temperature range        from room temperature to approximately 200° C.;    -   the halogenation reaction being performed in a temperature from        approximately 20° C. to approximately 150° C.;    -   the halogenation reaction being performed in a temperature from        approximately 20° C. to approximately 120° C.;    -   the halogenation reaction being performed in a temperature from        approximately 20° C. to approximately 100° C.;    -   the halogenation reaction being performed in a temperature from        approximately 25° C. to approximately 150° C.;    -   the halogenation reaction being performed in a temperature from        approximately 25° C. to approximately 120° C.;    -   the halogenation reaction being performed in a temperature from        approximately 25° C. to approximately 100° C.;    -   the halogenation reaction being performed in a temperature from        approximately 25° C. to approximately 65° C.;    -   the halogenation reaction being performed in a temperature from        approximately 50° C. to approximately 120° C.;    -   the halogenation reaction being performed in a temperature from        approximately 70° C. to approximately 120° C. in the presence of        catalyst;    -   the halogenation reaction being performed in a temperature from        approximately 40° C. to approximately 70° C. in the presence of        catalyst;    -   the halogenation process being performed in a batch reactor or        in a flow reactor with or without catalyst;    -   a batch process being applied for syntheses of the        halosilazanes;    -   the batch process being performed in a batch reactor comprising        of the steps of:        -   a. preparing a solution of a halogenation agent in a            suitable solvent with or without a catalyst in the reactor;        -   b. adding the solution into the reactor;        -   c. charging the reactor with the hydrosilazane with or            without a solvent;        -   d. stirring the obtained mixture with or without heating            while monitoring the reaction progress;        -   e. isolating the product by distillation straight from the            reactor or directing the reaction mix (with optional            filtration) into a separate distillation unit that allows:            -   i. isolating of the unreacted starting material(s);            -   ii. isolating of the chlorinated silazane product(s);            -   iii. isolating of the byproducts (optional);            -   iv. recovering the solvent (optional);        -   f. directing the isolated starting material, the recovered            solvent and the catalyst (optional) into the steps a and b.    -   a flow process being applied for syntheses of the halosilazanes;    -   the flow process being performed in a flow reactor comprising of        the steps of:        -   a. preparing a solution of the halogenation agent (e.g.,            Ph₃C(X) in a suitable solvent;        -   b. adding the hydrosilazane (e.g., TSA) and the solution of            the halogenation agent in a suitable solvent into the flow            reactor;        -   c. recirculation of reaction mixture consisting of TSA and            the solution of the halogenation agent in the suitable            solvent through the flow reactor, while monitoring degree of            conversion to TSA-X (X=F, Cl, Br or I) by means of Raman            Spectroscopy;        -   d. delivering the reaction mixture into the receiver,            cooling the reaction mixture for precipitation of unreacted            halogenation agent (Ph₃C(X));        -   e. filtration of the unreacted halogenation agent;        -   f. delivering the reaction mixture in a crude distillation            setup;        -   g. isolating the product halosilazanes by distillation that            allows:            -   1) isolating of the unreacted starting material(s)                (e.g., TSA);            -   2) isolating of the product halosilazanes, (e.g.,                TSA-X);            -   3) isolating of byproducts (e.g., TSA-X₂), and/or other                aminosilanes; and            -   4) recovering the solvent;        -   h. directing the products (TSA-X) into UHP distillation            setup that allows isolation of UHP products; and        -   i. alternatively, directing the products (TSA-X) into            reactor for synthesis of aminosilanes from the product            halosilazanes, (e.g., TSA-X) and a suitable amine.    -   approximately 5% to approximately 80% of the starting inorganic        hydrosilazanes being converted to the halogenated counterpart.    -   approximately 10% to approximately 50% of the starting inorganic        hydrosilazanes being converted to the halogenated counterpart.    -   the pressure of the halogenation process ranging from        approximately 0 to approximately 50 psig;    -   the pressure of the halogenation process ranging from        approximately 0 to approximately 20 psig;    -   monitoring the reaction progress by Raman spectroscopy using an        internal or an external Raman probe;    -   the produced halosilazanes being isolated from the reaction        mixture by a distillation, crystallization or filtration        processes;    -   the produced halosilazanes being isolated from the reaction        mixture by a fractional distillation;    -   the pressure during the fractional distillation being from        approximately 0.1 torr to approximately 760 torr;    -   the pressure during the fractional distillation being from        approximately 1 torr to approximately 100 torr;    -   the temperature during the fractional distillation being from        approximately 20° C. to approximately 100° C.;    -   the temperature during the fractional distillation being from        approximately 25° C. to approximately 65° C.;    -   the solvent and unreacted starting compounds being used for the        next batch;    -   the produced halosilazanes being used with or without isolation        or deep purification for further syntheses;    -   the halogenation process being monitored by Raman spectroscopy,        Gas chromatography or any other suitable means;    -   in a flow process, the degree of conversion of hydrosilazanes to        halosilazanes being monitored by on-line Raman spectroscopy and        the reaction mixture being recirculated through the flow reactor        until the desired degree of conversion is achieved; and    -   the flow process being performed under an inert atmosphere, such        as N₂, a noble gas (i.e., He, Ne, Ar, Kr, Xe), or combinations        thereof.

Also disclosed are nitrogen-doped silicon oxide films formed by theprocess of introducing into a reactor containing a substrate a vaporincluding a mono-substituted TSA precursor to form a silicon-containinglayer on the substrate; reacting an oxidizing agent with thesilicon-containing layer to form an oxidized silicon-containing layer byintroducing the oxidizing agent into the reactor; reacting themono-substituted TSA precursor with the oxidized silicon-containinglayer to form a silicon-rich oxidized silicon-containing layer byintroducing the mono-substituted TSA precursor into the reactor; andreacting a nitrogen-containing reactant with the silicon-containinglayer to form the nitrogen-doped silicon oxide film by introducing thenitrogen-containing reactant into the reactor. The mono-substituted TSAprecursors have a formula (SiH₃)₂N—SiH₂—X, wherein X is selected from ahalogen atom selected from Cl, Br or I; an isocyanato group [—NCO]; anamino group [—NR¹R²]; a N-containing C₄-C₁₀ saturated or unsaturatedheterocycle; or an alkoxy group [—O—R]; R¹, R² and R each is selectedfrom H; a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbylgroup; or a silyl group SiR′₃ with each R¹ being independently selectedfrom H; a halogen atom selected from Cl, Br, or I; a C₁-C₄ saturated orunsaturated hydrocarbyl group; a C₁-C₄ saturated or unsaturated alkoxygroup; or an amino group —NR³R⁴ with each R³ and R⁴ being selected fromH or a C₁-C₅ linear or branched, saturated or unsaturated hydrocarbylgroup, provided that if R¹=H, then R²≠H or Me. The process to producethe disclosed nitrogen-doped silicon oxide films may include one or moreof the following aspects;

-   -   purging the reactor with an inert gas between each introduction        step;    -   the mono-substituted TSA precursor wherein X is a halogen atom;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—Cl;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—Br;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—I;    -   the mono-substituted TSA precursor wherein X is a isocyanate        —NCO (i.e., being (SiH₃)₂N—SiH₂—NCO);    -   the mono-substituted TSA precursor wherein X is an amino group        [—NR¹R²];    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NiPr₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NHiPr;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NHtBu;    -   the mono-substituted TSA precursor not being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHEt)) (i.e., when X=NR¹R² and R¹ is        SiH₃ and R² is NHEt);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—NEt₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NEtMe;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NMe₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NMeiPr;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂ NEtiPr;    -   the mono-substituted TSA precursor wherein X is —N(SiR₃)₂,        wherein each R is independently selected from a halogen. H. or a        C₁-C₄ alkyl group;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiCl₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiBr₃)₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—N(SiI₃)₂;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—N(SiH₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂Cl);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NEt₂);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NiPr₂);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHtBu);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂OEt);    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂OiPr);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiMe₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—NH(SiMe₃);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂—N(SiEt₃)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂Et)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂iPr)₂;    -   the mono-substituted TSA precursor being        (SiH₃)₂—N—SiH₂—N(SiMe₂nPr)₂;    -   the mono-substituted TSA precursor wherein X is a N-containing        C₄-C₁₀ heterocycle;    -   the mono-substituted TSA precursor wherein the N-containing        C₄-C₁₀ heterocycle is selected from pyrrolidine, pyrrole, and        piperidine;    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(pyrrolidine);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(pyrrole);    -   the mono-substituted TSA precursor being        (SiH₃)₂N—SiH₂-(piperidine);    -   the mono-substituted TSA precursor wherein X is an alkoxy group        [—O—R];    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OH);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OMe);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OEt);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OiPr);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OnPr);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OtBu);    -   the mono-substituted TSA precursor wherein X is —O—SiR₃ and each        R is independently selected from H, a halogen, or a C₁-C₄        hydrocarbyl group;    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiH₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiCl₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiBr₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiI₃);    -   the mono-substituted TSA precursor being (SiH₃)₂N—SiH₂—(OSiMe₃);    -   the reactant being selected from the group consisting of O₂, O₃,        H₂O, H₂O₂, NO, NO₂, a carboxylic acid, an alcohol, a diol,        radicals thereof, and combinations thereof; and    -   the reactant being selected from the group consisting of N₂, H₂,        NH₃, hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic        amines (such as NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃,        (SiMe₃)₂NH), pyrazoline, pyridine, diamines (such as ethylene        diamine), radical species thereof, and mixtures thereof.

Notation and Nomenclature

The following detailed description and claims utilize a number ofabbreviations, symbols, and terms, which are generally well known in theart. While definitions are typically provided with the first instance ofeach acronym, for convenience, Table 1 provides a list of theabbreviations, symbols, and terms used along with their respectivedefinitions.

TABLE 1 a or an One or more than one Approximately ±10% of the valuestated or about LCD-TFT liquid-crystal display-thin-film transistor MlMMetal-insulator-metal DRAM dynamic random-access memory FeRamFerroelectric random-access memory OLED organic light-emitting diode CVDchemical vapor deposition LPCVD low pressure chemical vapor depositionPCVD pulsedchemical vapor deposition SACVD sub-atmospheric chemicalvapor deposition PECVD plasma enhanced chemical vapor deposition APCVDatmospheric pressure chemical vapor deposition HWCVD hot-wire chemicalvapor deposition FCVD flowable chemical vapor deposition MOCVD metalorganic chemical vapor deposition ALD atomic layer deposition spatialALD spatial atomic layer deposition HWALD hot-wire atomic layerdeposition PEALD plasma enhanced atomic layer deposition sccm standardcubic centimeters per minute MP melting point TGA thermogravimetricanalysis SDTA simultaneous differential thermal analysis GCMS gaschromatography-mass spectrometry TSA trisilylamine SRO strontiumruthenium oxide HCDS hexachiorodisilane PCDS pentachlorodisilane OCTSn-octyltrimethoxysilane MCS monochlorosilane DCS dichlorosilane TSATrisilylamine DSA disilylamine TriDMAS or tris(dimethylamino)silane orSiH(NMe₂)₃ TDMAS BDMAS bis(dimethylamino)silane or SiH₂(NMe₂)₂ BDEASbis(diethylamino)silane or SiH2(NEt₂)₂ TDEAS tris(diethylamino)silane orSiH(NEt₂)₃ TEMAS tris(ethylinethylamino)silane or SiH(NEtMe)₃ TMAtrimethyl aluminum or AlMe₃ PET polyethylene terephthalate TBTDEN(tert-butylimido)bis(dimethylamino)niobium or Nb(═NtBu)(NMe₂)₂ PENpolyethylene naphthalate PEDOT:PSS poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) Alkyl group saturated functional groupscontaining exclusively carbon and hydrogen atoms, including linear,branched, or cyclic alkyl groups Me Methyl Et Ethyl iPr isopropyl arylaromatic ring compounds where one hydrogen atom has been removed fromthe ring heterocycle cyclic compounds that has atoms of at least twodifferent elements as members of its ring PTFE Polytetrafluoroethylene

As used herein, hydrosilazanes refer to linear or branched analogs of ageneral formulae (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)) (where a,n≥1). For example, TSA (n=1, a=1), bis(disilylamino)silane (BDSASi,(SiH₃)₂—N—SiH₂—N—(SiH₃)₂) (n=2, a=1), tris(disilanyl)amine (n=1, a=2),cyclic silazanes {(SiH₃)N(SiH₂)}_(n) (with n>2) (e.g.,N,N′,N″trisilylcydotrisilazane {(H₃Si)N(SiH₂)}₃ (n=3)). Thehydrosilazanes are silazanes containing combinations of a and n in theabove formulae as well as silazanes containing catenated Si atoms.

As used herein, inorganic hydrosilazanes of general formula(SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) (n≥1, each a, b isindependently 0 to 3, a+b=3, R=alkyl group) include TSA (n=1, a=3, b=0),bis(disilylamino)silane (n=2, a=3, b=0), diethylaminotrisilylamine (n=1,a=3, b=0 and a=2, b=1, R=E_(t)), diisopropylaminotrisilylamine (n=1,a=3, b=0 and a=2, b=1, R=^(i)Pr), diisobutylaminotrisilylamine (n=1,a=3, b=0 and a=2, b=1, R=^(i)Bu), tertbutylaminotrisilylamine orsilanediamine, N′-(1,1-dimethylethyl)-N, N-disilyl- (n=1, a=3, b=0 anda=2, b=1, R=^(i)Bu and H). The term “inorganic hydrosilazanes” is usedbecause silicon atoms are connected to at least one hydrogen atom andnitrogen atom, the silicon atoms may be connected to halogen atom butare not connected to carbon atoms.

Throughout the present context, “X” is used to represent halogenelements, F, Cl, Br or I.

In the present context, a heterogeneous catalyst is understood to mean acatalyst that is present in a different phase from the reactants. It canbe combined with a substrate, which is intrinsically inert or lessactive (compared to the catalyst material) for this chemical reaction(the “support”). A homogeneous catalyst is understood to mean a catalystthat is present in the same phase as the reactants.

As used herein, “room temperature” in the text or in a claim means fromapproximately 20° C. to approximately 25° C.

The term “wafer” or “patterned wafer” refers to a wafer having a stackof silicon-containing films on a substrate and a patterned hardmasklayer on the stack of silicon-containing films formed for pattern etch.

The term “substrate” refers to a material or materials on which aprocess is conducted. The substrate may refer to a wafer having amaterial or materials on which a process is conducted. The substratesmay be any suitable wafer used in semiconductor, photovoltaic, flatpanel, or LCD-TFT device manufacturing. The substrate may also have oneor more layers of differing materials already deposited upon it from aprevious manufacturing step. For example, the wafers may include siliconlayers (e.g., crystalline, amorphous, porous, etc.), silicon containinglayers (e.g., SiO₂, SiN, SiON, SiCOH, etc.), metal containing layers(e.g., copper, cobalt, ruthenium, tungsten, platinum, palladium, nickel,ruthenium, gold, etc.) or combinations thereof. Furthermore, thesubstrate may be planar or patterned. The substrate may be an organicpatterned photoresist film. The substrate may include layers of oxideswhich are used as dielectric materials in MEMS, 3D NAND, MIM, DRAM, orFeRam device applications (for example, ZrO₂ based materials, HfO₂ basedmaterials, TiO₂ based materials, rare earth oxide based materials,ternary oxide based materials, etc.) or nitride-based films (forexample, TaN, TiN, NbN) that are used as electrodes. One of ordinaryskill in the art will recognize that the terms “film” or “layer” usedherein refer to a thickness of some material laid on or spread over asurface and that the surface may be a trench or a line. Throughout thespecification and claims, the wafer and any associated layers thereonare referred to as substrates.

The term of “deposit” or “deposition” refers to a series of processeswhere materials at atomic or molecular levels are deposited on a wafersurface or on a substrate from a gas state (vapor) to a solid state as athin layer. Chemical reactions may be involved in the process, which mayoccur after creation of a plasma of the reacting gases. The plasma maybe a CCP, as described above, generally created by radio frequency (RF)(alternating current (AC)) frequency or direct current (DC) dischargebetween two electrodes, the space between which is filled with thereacting gases. The deposition methods may include atomic layerdeposition (ALD) and chemical vapor deposition (CVD).

The term “mask” refers to a layer that resists etching. The hardmasklayer may be located above the layer to be etched.

The term “aspect ratio” refers to a ratio of the height of a trench (oraperture) to the width of the trench (or the diameter of the aperture).

The term “selectivity” means the relative selectivity of halogenationprocess (e.g., TSA-Cl as a halogenating agent) expressed as aselectivity coefficient (r) from GC chromatogram, wherein:r(%)=I _(TSA-Cl)/(I _(TSA-Cl) +ΣI _((all side products))).where I_(TSA-Cl) is the intensity of TSA-Cl signal in GC chromatogram ofproducts, ΣI_((all side products)) is sum of the intensities of all sideproducts, which may include SiH₄, MCS, DCS, (H₃Si)₂N(SiHCl₂),(H₃Si)N(SiH₂Cl)₂. (H₃Si)N(SiH₂)N(SiH₃)₃, other chlorinated andnon-chlorinated TSA oligomers.

Note that herein, the terms “film” and “layer” may be usedinterchangeably. It is understood that a film may correspond to, orrelated to a layer, and that the layer may refer to the film.Furthermore, one of ordinary skill in the art will recognize that theterms “film” or “layer” used herein refer to a thickness of somematerial laid on or spread over a surface and that the surface may rangefrom as large as the entire wafer to as small as a trench or a line.

The standard abbreviations of the elements and standard names of groupsof elements from the periodic table of elements are used herein. Itshould be understood that elements may be referred to by theseabbreviations (e.g., Si refers to silicon, N refers to nitrogen, Orefers to oxygen, C refers to carbon, H refers to hydrogen, F refers tofluorine, Hal refers to halogens, which are F, Cl, Br or I, At, etc.).

The unique CAS registry numbers (i.e., “CAS”) assigned by the ChemicalAbstract Service are provided to identify the specific moleculesdisclosed.

Please note that the silicon-containing films, such as SiN and SiO, arelisted throughout the specification and claims without reference totheir proper stoichiometry. The silicon-containing films may includepure silicon (Si) layers, such as crystalline Si, poly-silicon (p-Si orpolycrystalline Si), or amorphous silicon; silicon nitride (Si_(k)N_(l))layers; or silicon oxide (Si_(n)O_(m)) layers; or mixtures thereof,wherein k, l, m, and n, inclusively range from 0.1 to 6. Preferably,silicon nitride is Si_(k)N_(l), where k and l each range from 0.5 to1.5. More preferably silicon nitride is Si₃N₄. Herein, SiN in thefollowing description may be used to represent Si_(k)N_(l) containinglayers. Preferably silicon oxide is Si_(n)O_(m), where n ranges from 0.5to 1.5 and m ranges from 1.5 to 3.5. More preferably, silicon oxide isSiO₂. Herein, SiO in the following description may be used to representSi_(n)O_(m) containing layers. The silicon-containing film could also bea silicon oxide based dielectric material such as organic based orsilicon oxide based low-k dielectric materials such as the Black DiamondII or III material by Applied Materials, Inc. with a formula of SiOCH.Silicon-containing film may also include Si_(a)O_(b)N_(c) where a, b, crange from 0.1 to 6. The silicon-containing films may also includedopants, such as B, C, P, As and/or Ge.

Ranges may be expressed herein as from about one particular value,and/or to about another particular value. When such a range isexpressed, it is to be understood that another embodiment is from theone particular value and/or to the other particular value, along withall combinations within said range.

Reference herein to “one embodiment” or “an embodiment” means that aparticular feature, structure, or characteristic described in connectionwith the embodiment may be included in at least one embodiment of theinvention. The appearances of the phrase “in one embodiment” in variousplaces in the specification are not necessarily all referring to thesame embodiment, nor are separate or alternative embodiments necessarilymutually exclusive of other embodiments. The same applies to the term“implementation.”

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula MR¹ _(x) (NR²R³)_((4−x)), where x is 2or 3, the two or three R¹ groups may, but need not be identical to eachother or to R² or to R³. Further, it should be understood that unlessspecifically stated otherwise, values of R groups are independent ofeach other when used in different formulas.

BRIEF DESCRIPTION OF THE FIGURES

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying figure wherein:

FIG. 1 is a diagram of the Picosun R200 PEALD 8″ deposition tool used toperform the depositions in Examples 4-6;

FIG. 2 is a graph the ALD growth rate of silicon oxide films as afunction of the number of precursor pulses using the precursor(SiH₃)₂N—SiH₂—NiPr₂;

FIG. 3 is a graph of the ALD growth rate of silicon oxide thin film as afunction of the temperature using the precursor (SiH₃)₂N—SiH₂—NiPr₂;

FIG. 4 is a graph the ALD growth rate of silicon oxide films as afunction of the number of precursor pulses and the temperature using theprecursor (SiH₃)₂N—SiH₂—N(SiH₃)₂;

FIG. 5 is a diagram of the batch process for catalytic or non-catalyticpreparation of TSA-X;

FIG. 6 is a diagram of the flow process for catalytic or non-catalyticpreparation of TSA-X;

FIG. 7 is a GC chromatogram of solution Ph₃CCl-TSA and Pd/C₁₋₄ h 20 minheating illustrating selectivity of chlorination toward the TSA-Cl;

FIG. 8 is a GC chromatogram of solution Ph₃CCl-TSA and Pt/C₁₋₄ h 20 minheating illustrating selectivity of chlorination toward the TSA-Cl;

FIG. 9 is a GC chromatogram of solution Ph₃CCl-TSA and BPh₃, 4 h 15 minheating illustrating selectivity of chlorination toward the TSA-Cl;

FIG. 10 is Kinetic of TSA-Cl accumulation in reaction mixtures invarious solvents;

FIG. 11 is Mass Spectra of BDSASi-Br main isomer;

FIG. 12 is a GC chromatogram of BDSASi reaction mixture of 1MPh₃CBr/CH₂Cl₂+1.45 eq.;

FIG. 13 is Mass Spectra of BDSASi-Cl main isomer;

FIG. 14 is Mass Spectra of BDSASi-Cl₂ main isomer;

FIG. 15 is a GC chromatogram of BDSASi reaction mixture of 1MPh₃CCl/CH₂Cl₂+1.45 eq.;

FIG. 16 is a GC chromatogram of TSA-Cl reaction mixture of 1MPh₃CBr/CH₂Cl₂+1.45 eq.; and

FIG. 17 is a GC chromatogram of reaction mixture after chlorination of(H₃Si)₂N(SiH₂(N^(i)Pr₂)).

DESCRIPTION OF PREFERRED EMBODIMENTS

Disclosed are Si-containing film forming compositions comprisinghalosilazane or inorganic halosilazane or halogenated hydrosilazaneprecursors having a general formula:(SiH_(a)(NR₂)_(b)X_(c))_((n+2))N_(n)(SiH_((2−d))X_(d))_((n−1))  (I)where X is selected from a halogen atom selected from F, Cl, Br or I; Reach is selected from, saturated or unsaturated hydrocarbyl group.Preferably, R is an alkyl group selected from Me, Et, Pr, ^(i)Pr, Bu,^(i)Bu, or ^(t)Bu.

When the H, a C₁-C₆ linear or branched, saturated or unsaturatedhydrocarbyl group, or a silyl group [SiR′₃]; and each a, b, c isindependently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1. In the subgenuscomprising a silyl group [SiR′₃], each R′ is independently selected fromH, a halogen atom selected from F, Cl, Br or I, a C₁-C₄ saturated orunsaturated hydrocarbyl group, a C₁-C₄ saturated or unsaturated alkoxygroup, or an amino group [—NR¹R²] with each R¹ and R² being furtherselected from H or a C₁-C₆ linear or branched disclosed halosilazane orhalogenated hydrosilazane precursors do not contain R, the disclosedhalosilazane or halogenated hydrosilazane precursors are carbon-freehalosilazanes having a general formula:(Si_(a)H_(2a+1))_(n+2−c)(Si_(a)H_(2a+1−m)X_(m))_(c)N_(n)(SiH₂)_((n−1−d))(SiH_(2−b)X_(b))_(d)  (II)where X is a halogen atom selected from F, Cl, Br or I; a, n≥1;0<m<2a+1; b=0-2; 0<c<n+2 and 0≥d<n−1.

The disclosed Si-containing film forming compositions have a number ofsilicon atoms higher than 1, and preferably higher than 2, without adirect Si—C bond, and are polar molecules. Volatility and lack of Si—Cbond in the structure of the disclosed halosilazane precursors result insuitability for use in applications for film deposition of high puritysilicon oxide, silicon nitride, silicon oxinitride, or the like, by CVDand ALD and other deposition methods.

The disclosed Si-containing film forming compositions, when n=1, include(H₃Si)₂N(SiH₂Cl), (H₃Si)₂N(SiH₂Br), (H₃Si)N(SiH₂Br)₂, (H₃Si)₂N(SiH₂I),(H₃Si)N(SiH₂Cl)₂, (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Cl),(H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Br), (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂I),(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)), (H₃Si)(H₂SiBr)N(SiH₂(N^(i)Pr₂)),(H₃Si)(H₂SiI)N(SiH₂(N^(i)Pr₂)), (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)).(H₃Si)(H₂SiBr)N(SiH₂(NEt₂)), (H₃Si)(H₂SiI)N(SiH₂(NEt₂)),(H₂SiCl)₂N(SiH₂(N^(i)Pr₂)), (H₃SiCl)N(SiH₂(N^(i)Pr₂))₂,(H₂SiCl)N(SiH₂(NEt₂))₂, (H₂SiCl)₂N(SiH₂(N^(i)Pr₂)),(H₃SiCl)N(SiH₂(N^(i)Pr₂))₂ and (H₂SiCl)N(SiH₂(NEt₂))₂.

The disclosed Si-containing film forming compositions, when n=2, include(H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Cl), (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Br) and(H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂I).

The disclosure also includes methods of preparation of the disclosedSi-containing film forming compositions, that is, methods of preparationof the disclosed halosilazanes or halosilazane precursors, which referto methods of selective halogenation of hydrosilazanes (aminosilanes).The disclosed halosilazane precursors in formula (I) may be producedthrough the methods of selective halogenation of hydrosilazanes(aminosilanes) having a general formula(SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1))  (III)where R each is selected from H, a C₁-C₆ linear or branched, saturatedor unsaturated hydrocarbyl group, or a silyl group [SiR′₃]; each a, b isindependently 0 to 3; a+b=3. In the ated hydrocarbyl group, a C₁-C₄saturated or unsaturated alkoxy group, or an amino subgenus comprising asilyl group [SiR′₃], each R′ is independently selected from H, a halogenatom selected from F, Cl, Br or I, a C₁-C₄ saturated or unsaturroup[—NR¹R²] with each R¹ and R² further being selected from H or a C₁-C₆linear or branched, saturated or unsaturated hydrocarbyl group; n≥1.Preferably, R is an alkyl group selected from Me, Et, Pr, ^(i)Pr, Bu,^(i)Bu, or ^(t)BU.

The carbon-free halosilazanes may be produced through the methods ofselective halogenation of hydrosilazanes (aminosilanes) having a generalformula(Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1))  (IV)where a, n≥1.

The disclosed (H₃Si)₂N(SiH₂Cl), (H₃Si)₂N(SiH₂Br), (H₃Si)₂N(SiH₂I) and(H₃Si)N(SiH₂Cl)₂ may be produced by selective halogenation of TSA.

The disclosed (H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)),(H₃Si)(H₂SiBr)N(SiH₂(N^(i)Pr₂)) and (H₃Si)(H₂SiI)N(SiH₂(N^(i)Pr₂)) maybe produced by selective halogenation of diisopropylaminotrisilylamine.

The disclosed (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)), (H₃Si)(H₂SiBr)N(SiH₂(NEt₂))and (H₃Si)(H₂SiI)N(SiH₂(NEt₂)) may be produced by selective halogenationof diethylaminotrisilylamine.

The disclosed (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Cl),(H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Br) and (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂I) may beproduced by selective halogenation of bis(disilylamino)silane.

Due to a high susceptibility of Si—N bond in inorganic hydrosilazanes ofthe general formula (I) and carbon-free halosilazanes of the generalformula (II), various reagents may attack these compounds duringhalogenation process, thereby greatly reducing yield of these compounds(See, Advances in Inorganic Chemistry and Radiochemistry, Vol. 3,Academic Press, Inc., NY, 1961). The well-known halogenationmethods/reagents suitable for silanes (See, Inorganic Reactions andMethods. Vol. 3, Part 1: Formation of Bonds to Halogens, VCHP, 1989, NY)turn out to be not industrially applicable for hydrosilazanes. The priorart described above discloses desilylative coupling trigged by Lewisacid/base and Si—N bond cleavages during the halogenation process ofhydrosilazanes.

Thus, in order to halogenate inorganic hydrosilazanes(SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) (III) and carbon-freehydrosilazanes (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)) (IV),selectively and with a reasonable yield, the utilized chemical reagents(e.g., halogenating agents, catalysts and solvents) should not bestrongly electro- or nucleophilic, should not form strongly electro- ornucleophilic byproducts by interaction with silane and should not formacids (such as HCl, HBr) by interaction with silane or reactionbyproducts.

It is known halocarbons C_(x)H_(y)(X)₂ (X=F, Cl, Br or I) do not exhibitstrong electro- or nucleophilic properties and may be utilized forhalogenation of organic silanes. According to the prior art, halocarbonssuch as CHCl₃, Ph₃CCl, Ph₃CBr have been utilized for halogenation ofaryl-, alkyl-, alkoxy- and chlorosilanes. These silanes however are muchmore robust and less susceptible to side reactions comparing tohydrosilazanes disclosed therein. To our knowledge, no examples ofselective halogenation of inorganic hydrosilazanes(SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) (III) and carbon-freehydrosilazanes (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1)) (IV) by theabove mentioned agents have been found in the prior art.

As shown in the comparative examples below, when applied to inorganichydrosilazanes (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) (III) andcarbon-free hydrosilazanes (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1))(IV), the aforementioned halogenation procedures result in low yield(below 5% for cases with C₂Cl₆, CH₂Cl₂ and other chlorocarbons),irreproducible and low reaction rates (for Ph₃CCl in toluene), andnon-selective halogenation reaction (with Ph₃CCl, C₂Cl₆ in toluene andneat TSA).

Thus, a selection of the halogenation reagents, catalysts, ratio ofstarting compounds and the reaction conditions (e.g., type of solvent,concentrations, temperature, pressure) for achieving the bestselectivity of halogenation of hydrosilazanes is important for achievinghigher reaction yields.

In one embodiment, a halogenation reagent, trityl halides, Ph₃C(X)(X=Cl, Br, I) is selected for selective halogenation of inorganichydrosilazanes (SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)) (III) andcarbon-free hydrosilazanes (Si_(a)H_(2a+1))_((n+2))N_(n)(SiH₂)_((n−1))(IV). In one embodiment, it is preferred to have 1.5-10 molar excess ofhydrosilazanes relative to trityl halides for selective preparation ofmonohalogenated compounds(Si_(a)H_(2a+1))_(n+1)(Si_(a)H_(2a)(X))N_(n)(SiH₂)_((n−1)) or(SiH_(a)(NR₂)_(b)(X))(n+₂)N_(n)(SiH₂)_((n−1)).

Solvent selection is also important for industrial processes. Asreported in the prior art, halogenation proceeds could be faster inchlorinated media such as dichloromethane, chloroform ortetrachloroethane than other media. Due to hazardous natures of thesesolvents, their usage is highly regulated. In one embodiment,halogenated chlorocarbon solvents are utilized and then recycled afterthe reaction for next use, thereby leading to a process with the minimalamount of hazardous waste. Generally, less hazardous solvents such astoluene, anisole or heptane are highly recommended compared tochlorocarbons and benzene. (See “Solvent selection guide and ranking: Asurvey of solvent selection guides”, Denis Prat, John Hayler, AndyWells, Green Chem., 2014, 16, 4546-4551).

In one embodiment, the disclosed solvents include aromatic solvents suchas toluene, xylene, mesitylene with or without a catalyst at certainconditions.

The disclosed methods of selective halogenation of hydrosilazanesprovide practical/scalable synthesis methods of the aforementionedcompounds, as shown in formula (III) and (IV), through tuning andoptimizing reaction conditions that favor a product high yield andminimize effects of side reactions. In one embodiment, mono-halogenatedTSA derivatives are selectively synthesized with a high yield innon-halogenated arene solvents such as toluene from TSA and tritylhalides by using 1.54 molar excess of TSA and heating the reactionmixture for a certain time in a range of 80° C.-100° C. under a pressureof 10-20 psig. Alternatively, the selective halogenation with a highyield may be achieved at a certain time duration at room or moderatetemperature up to 52° C. and atmospheric pressure applying a catalyst.

The disclosed catalysts include homogeneous catalysts, such as BPh₃,B(SiMe₃)₃ or the like and heterogeneous catalysts, such as, Ru, Pt, Pdin elemental form or on support deposited on an inert surface of carbon,silica, alumina, molecular sieves, or the like. The disclosed catalystsdo not possess strong electro- or nucleophilicity, and do not formacids, or strong electro- or nucleophilic byproducts by interaction withhydrosilazanes. The disclosed catalysts are thermally stable andaccelerate the reactions in hydrocarbon solvents such as toluene orxylene as shown in examples that follow.

In one embodiment, the catalyst selectively accelerates transformationof hydrosilazanes into halogenated counterparts, where halogens are F,Cl, Br or I. The preferred selectivity of the process is achieved whenthe catalyst converts approximately 5% to approximately 70% halogenatingagent (e.g., chlorinating agent), preferably approximately 10% toapproximately 70% of halogenating agent, more preferably approximately20 to approximately 60% of halogenating agent, even more preferablyapproximately 25% to approximately 60% of halogenating agent. Afterconversion, the catalyst, unreacted starting hydrosilazane, halogenatingagent, and halogenated hydrosilazane are separated from a reactionmixture by distillation, crystallization or filtration processes. Theapproximate amount of catalyst generally varies from 0.1 to 10 mol %relative to the halogenating agent, preferably from 2 to 6 mol %.

The disclosed methods of selective halogenation of hydrosilazanesincludes temperature ranges for optimizing the yield of halogenatedsilazane and the selectivity of process. A halogenation rate with a highselectivity for halogenation process without a catalyst is achieved inthe temperature range from approximately 20° C. to approximately 200°C., preferably 50° C. to 120° C., more preferably from 70° C. to 90° C.The disclosed temperature ranges may be higher than boiling point ofcertain substrates (e.g. boiling point of TSA is 53° C.). Hence theprocess is performed at an above-atmospheric pressure in a closedsystem. The pressure in the process may vary from approximately 0 toapproximately 50 psig, preferably from approximately 5 to approximately20 psig. The temperature and pressure in the process are maintained by aproper selection of heating element, temperature control unit andpressure regulator.

In embodiments applying a catalyst, a halogenation rate with a highselectivity is achieved in a temperature range from approximately 20° C.to approximately 90° C., preferably from approximately 40° C. to 70° C.

The halogenation process may be performed in a batch reactor or in aflow reactor with or without catalyst. The preferred selectivity of theprocess is achieved when approximately 5% to approximately 80%, morepreferably approximately 10% to approximately 50% of the startinginorganic hydrosilazanes are converted to the halogenated counterpart.The degree of conversion may be monitored in-situ by GC, Ramanspectroscopy or any other suitable technique. When a required degree ofconversion is achieved, the reaction mixture is separated by usingcommon techniques, such as distillation, crystallization and filtration.The product(s) is (are) isolated while the unreacted startingmaterial(s), solvent and catalyst may be recycled or reused.

The disclosed methods of selective halogenation of hydrosilazanes mayhave a selectivity of halogenation of the hydrosilazane ranging fromapproximately 30% to approximately 100%, preferably, a selectivity ofhalogenation of the hydrosilazane ranging from approximately 70% toapproximately 97%, more preferably, a selectivity of halogenation of thehydrosilazane ranging from approximately 80% to approximately 91%.

The disclosed methods of selective halogenation of hydrosilazanes mayprovide a yield of halogenation of the hydrosilazane ranging fromapproximately 30% to approximately 90%, preferably, a yield ofhalogenation of the hydrosilazane ranging from approximately 40% toapproximately 80%, more preferably, a yield of halogenation of thehydrosilazane ranging from approximately 50% to approximately 80%, evenmore preferably, a yield of halogenation of the hydrosilazane rangingfrom approximately 60% to approximately 80%. One skilled in the art mayrecognize that if providing enough excess of TSA in the aboveembodiment, a yield of halogenation of the hydrosilazane may approach100%. Thus, the disclosed methods of selective halogenation ofhydrosilazanes may provide a yield of halogenation of the hydrosilazaneranging from approximately 30% to 100%.

Fractional distillation may proceed at room temperature or by moderateheating in a temperature range from approximately 20° C. toapproximately 100° C., preferably from approximately 25° C. toapproximately 65° C. and at various pressure ranges. Ambient or reducedpressure from approximately 0.1 T to approximately 760 T or fromapproximately 1 T to approximately 100 T is preferred as it helps toreduce distillation temperature and suppress side reactions potentially.The side reactions lead to a lower yield of products.

Alternatively, the synthesized halogenated silazane(s) may be usedwithout isolation or deep purification for further chemicaltransformations.

The disclosed methods of selective halogenation of hydrosilazanesinclude a catalytic or non-catalytic process for preparation of targetedhalogenated hydrosilazanes (aminosilanes) by using commerciallyavailable starting materials and their further use with or withoutseparation/purification for their intended applications.

In one preferred embodiment, the disclosed halogenation ofhydrosilazanes shown in formula (III) and (IV) are conducted by theirtreatment with a solution of halogenating agent being trityl halides(Ph₃CX, X=F, Cl, Br or I) in a suitable solvent with or without acatalyst while performing the process in the temperature range from roomtemperature to approximately 200° C., preferably from room temperatureto approximately 120° C., more preferably from approximately 60° C. toapproximately 90° C., without the catalyst and in the temperature rangefrom approximately 40° C. to approximately 70° C. in the presence ofcatalyst in the batch or flow reactor. Progress of the reaction may bemonitored by Raman spectroscopy, Gas chromatography or any othersuitable means. Thus in a flow process, the degree of conversion ismonitored by on-line Raman spectroscopy and the reaction mixture isrecirculated through a reactor until the desired degree of conversion isachieved. The process may be conducted at atmospheric and higherpressure up to approximately 50 psig, preferably up to approximately 20psig and is regulated by proper equipment. The order of addition ofreagents may vary, e.g. silazane may be added to a solution ofchlorinating agent in the suitable solvent or vice versa; a stream ofsilazane may be added to a stream of chlorinating agent in a suitablesolvent and vice versa. Moderate temperatures below approximately 120°C. and pressures below approximately 50 psig allow the usage ofequipment with minimal capital investment. Separation of products isperformed by distillation. Chlorinated silazanes may be obtained in apure form, where the purity is more than 90% w/w, preferably more than98% w/w, or alternatively less pure chlorinated silazanes having purityfrom 60% w/w, preferably from 80% w/w may be directed to the reactor forsynthesis of other compounds, e.g. aminosilanes applying any suitableamine such as diisopropylamine, diethylamine, tert-butylamine.

In one embodiment, the synthesis and separation of the disclosedhalosilazanes or halogenated silazanes may be performed in a batchreactor comprising of steps:

-   -   a. preparing a solution of a halogenation agent in a suitable        solvent with or without a catalyst in the reactor;    -   b. adding the solution into the reactor;    -   c. charging the reactor with the hydrosilazane with or without a        solvent;    -   d. stirring the obtained mixture with or without heating while        monitoring the reaction progress;    -   e. isolating the product by distillation straight from the        reactor or directing the reaction mix (with optional filtration)        into a separate distillation unit that allows;        -   i. isolating of the unreacted starting material(s);        -   ii. isolating of the halogenated silazane product(s);        -   iii. isolating of the byproducts (optional);        -   iv. recovering the solvent (optional);    -   f. directing the isolated starting material, the recovered        solvent and the catalyst (optional) into the steps a and b.

FIG. 5 is a diagram of a batch process for catalytic or non-catalyticpreparation of TSA-X (X=F, Cl, Br or I), that is, a diagram of the batchprocess for catalytic or non-catalytic conversion of the silazane,particularly TSA, and Ph₃C(X) (X=F, Cl, Br or I) reactants to thehalogenated silazanes, in particular to TSA-Cl, TSA-Br. All of contactcomponents in the batch process need to be clean and air- andmoisture-free. The batch process may be performed under an inertatmosphere, such as N₂, a noble gas (i.e., He, Ne, Ar, Kr, Xe), acombinations thereof or any other dry/inert environment. Morespecifically, halogenating agent Ph₃C(X) (X=F, Cl, Br or I) 1 andsuitable solvent 2 are transferred via lines 3 and 4, respectively intomixing reactor 5 to prepare a halogenating agent solution. Optionally,catalyst 6 is added to mixing reactor 5 via line 7. Silazane (e.g., TSA(trisilylamine)) reactant 10 is added to batch reactor 9 via line 11.The halogenating agent solution formed in mixing reactor 8 is added tobatch reactor 9 via line 8. Silazane reactant 10 and the halogenatingagent solution formed in mixing reactor 5 (with or without a catalyst)may be added to batch reactor 9 by pump (not shown) or by pressuredifference.

Batch reactor 9 may be a typical vessel with means of agitation,temperature/pressure control and monitoring the reaction. Batch reactor9 is maintained at a temperature ranging from approximately roomtemperature or 25° C. to approximately 200° C., preferably fromapproximately room temperature or 25° C. to approximately 120° C., andthe corresponding pressure ranging from approximately 0.1 atm toapproximately 10 atm, preferably from approximately 1 atm toapproximately 5 atm. The reaction monitoring is provided bychromatographic (e.g. GC), spectroscopic (e.g. Raman) or any othersuitable analytical techniques.

After the desired range of conversion is achieved, the reaction mixturein batch reactor 9 is filtered with filter 12 (optional) from where theseparated heterogeneous catalyst is recycled via line 13. The filtrateis directed into distillation unit 14 to further isolate reactionproduct 15. Waste 18 is disposed while separated solvent 16 andunreacted silazane 17 may be recycled. Distillation unit 14 alsoseparates light by-products such as SiH₄, SiH₃Cl, SiH₂Cl₂, heavierby-products such as (H₃Si)₂N(SiHCl₂), (H₃Si)N(SiHCl)₂, {(H₃Si)₂N}₂(SiH₂)and other oligomeric aminosilanes. The by-products may be disposed orpurified and used. Alternatively, the crude reaction mixture may bedistilled directly from reactor 9 if it is equipped with the appropriatedistillation hardware (column, head, etc.).

Halogenated product 15 may be purified to any desirable level, e.g. upto 99.99% (ultra-high-purity (UHP)). The product of lower purity or eventhe crude reaction mixture without any purification may be utilized inthe following chemical processes if such processes are tolerable to lowpurity raw materials. For example, the low purity halogenated silazane(or a halosilazane-containing crude reaction mixture) may be reactedwith amines such as diethylamine, diisopropylamine, tert-butyl amine,dibutylamine, diisobutylamine, etc. to produce the correspondingaminosilanes. The solvents for this step may be selected from the abovementioned amines, toluene, hexane, heptane, etc.

In yet another embodiment, the synthesis and separation of the disclosedhalosilazanes or halogenated silazanes may be performed in a flowreactor comprising of steps:

-   -   a. preparing a solution of the halogenation agent (e.g.,        Ph₃C(X)) in a suitable solvent;    -   b. adding a hydrosilazane (e.g., TSA) and the solution of the        halogenation agent in a suitable solvent into the flow reactor;    -   c. recirculation of a reaction mixture consisting of the        hydrosilazane and solution of the halogenation agent in a        suitable solvent through the flow reactor, while monitoring        degree of conversion to a product halosilazane (e.g., TSA-X        (X=F, Cl, Br or I)) by means of Raman spectroscopy;    -   d. delivering the reaction mixture into a receiver, cooling the        reaction mixture and deposition of unreacted halogenation agent;    -   e. filtration of the unreacted halogenation agent;    -   f. delivering the reaction mixture in a crude distillation        setup;    -   g. isolating the product halosilazane by distillation that        allows:        -   1) isolating of the unreacted starting material(s);        -   2) isolating of the halogenated silazane product (i.e.,            halosilazane);        -   3) isolating of the byproducts (e.g., TSA-X₂), other            aminosilanes; and        -   4) recovering the solvent;    -   h. directing the halogenated silazane product (i.e.,        halosilazane) into UHP distillation setup that allows isolation        of UHP products; and    -   i. alternatively, directing the halogenated silazane product(s)        (i.e., halosilazane) into a reactor for synthesis of        aminosilanes from the halogenated silazane product (i.e.,        halosilazane) and a suitable amine.

FIG. 6 is a diagram of a flow process for catalytic or non-catalyticconversion of the silazane, particularly TSA, and Ph₃C(X) reactants tohalogenated silazanes, in particular to TSA-Cl, TSA-Br. All of thecontact components in the flow process need to be clean and air- andmoisture-free. The flow process may be performed under an inertatmosphere, such as N₂, a noble gas (i.e., He, Ne, Ar, Kr, Xe), orcombinations thereof. More specifically, a solution of halogenatingagent Ph₃C(X) 1 in suitable solvent 2 is prepared in mixing reactor 4.Silazane (e.g., TSA) reactant 3 and the solution of halogenating agentformed in mixing reactor 4 are added to flow reactor 8 via lines 5 and6, respectively. Silazane reactant 3 and the solution of halogenatingagent formed in mixing reactor 4 are then mixed in line 7 beforeintroduction into flow reactor 8. Silazane reactant 3 and the solutionof halogenating agent formed in mixing reactor 4 may be added to flowreactor 8 via a liquid metering pump (not shown), such as a diaphragmpump, peristaltic pump, or syringe pump or by pressure difference.Preferably, the mixing process is performed under an inert atmosphere atapproximately atmospheric pressure. Flow reactor 8 may be a tubularreactor with or without inert media such a glass wool, glass beds orequipped with the catalyst (list of catalyst provided in the nextsection). Flow reactor 8 may be maintained without catalyst at atemperature ranging from approximately 25° C. to approximately 200° C.,preferably from approximately 25° C. to approximately 120° C., or withcatalyst from approximately 60° C. to approximately 100° C., preferablyfrom approximately 40° C. to approximately 65° C. The temperatureselection may depend upon the catalyst selection, as well as the targetreaction products. Flow reactor 8 may be maintained at a pressureranging from approximately 0.1 atm to approximately 10 atm, preferablyfrom 1 atm to 5 atm. The flow of silazane reactant 3 and the solution ofhalogenating agent formed in mixing reactor 4 is selected to provideapproximately 5 minutes to approximately 100 minutes of residence timein flow reactor 8, alternatively between approximately 5 minutes toapproximately 20 minutes residence time. A flow of halogenated product11 from reaction mixture 9 after flow reactor 8 is directed to Ramanspectroscopy probe 10 and directed back in to flow reactor 8 if a yieldof halogenated product is within approximately 1 to approximately 20%.When a yield of halogenated product 11 is within approximately 20% toapproximately 100%, preferably from 20-60%, reaction mixture 9 iscollected in receiver 12. Receiver 12 may be any sort of trap,including, but is not limited to, dry ice/isopropanol, dry ice/acetone,refrigerated ethanol, and/or liquid nitrogen traps.

Similar to the batch process, the reaction mixtures in receiver 12 maybe collected in one or more containers and transported to a new locationprior to performance of the next process steps. Alternatively, thereaction mixtures in receiver 12 may be filtered from unreactedhalogenating agent 13, the halogenated product recovered, and thenimmediately directed to distillation unit 15 to further isolate thehalogenated product from reactants and reaction by-products.Distillation unit 15 separates halogenated product 20 from solvent 17,volatile reaction by-products 18, such as SiH₄, SiH₃Cl, SiH₂Cl₂, and anyunreacted silazane reactant 16 and heavier reaction products 19 such as(H₃Si)₂N(SiHCl₂), (H₃Si)N(SiHCl)₂₎ {(H₃Si)₂N}2(SiH₂), other oligomericaminosilanes. Unreacted silazane reactant 16 and solvent 17 may berecycled. Real time analysis and purification of unreacted silazanereactant 16 and solvent 17 may be provided to maintain quality ofdevices and monitoring equipment, during this continuous synthesisprocess, such as filters and/or in-situ GC, Raman spectroscopy analysis.

Similar to the batch process, halogenated product 20 in container 21 maybe transported to a new location prior to performance of the nextprocess steps. Alternatively, halogenated product 20 in container 21 maybe directed to UHP fractional distillation unit 22 to separate the UHPhalogenated product, whose purity is from 90 to 99.99% w/w, preferablyfrom 95 to 99.99% w/w, more preferably from 99.0 to 99.99% w/w. Afractional distillation may be formed with a static column or a spinningband column. The spinning band distillation column length is muchsmaller than that of the static column and may be preferred for use incrowded facilities because it takes up less space. Alternatively,halogenated product 20 in container 21, whose purity is fromapproximately 40% to approximately 90%, preferably from approximately70% to approximately 90%, may be directed to reactor 25 for synthesis ofother compounds, particularly for synthesis of aminosilanes with amine26 in suitable solvent 27. Amine 26 may be diethylamine,diisopropylamine, tert-butyl amine, dibutylamine, diisobutylamine, etc.solvent may be selected from above mentioned amines or toluene, hexane,heptane, etc.

The disclosed Si-containing film forming compositions also comprisemono-substituted TSA precursors having a Si—C bond free backbone and asingle chemically functionalized site to enable a high surfacereactivity. The mono-substituted TSA precursors having a number ofsilicon atoms higher than 1, and preferably higher than 2, without adirect Si—C bond, and being polar molecules may have an enhancedreactivity to a substrate surface to enable a fast deposition rate. Themono-substituted TSA precursors have the general formula:(SiH₃)₂N—SiH₂—Xwherein X is selected from a halogen atom selected from Cl, Br or I; anisocyanato group [—NCO]; an amino group [—NR¹R²]; a N-containing C₄-C₁₀saturated or unsaturated heterocycle; or an alkoxy group —O—R; each R¹,R² and R selected from a H; a silyl group (SiR′₃); or a C₁-C₆ linear orbranched, saturated or unsaturated hydrocarbyl group; with each R′ beingindependently selected from H; a halogen atom selected from Cl, Br, orI; a C₁-C₄ saturated or unsaturated hydrocarbyl group; a C₁-C₄ saturatedor unsaturated alkoxy group; or an amino group [—NR³R⁴], with each R³and R⁴ being independently selected from H or a C₁-C₆ linear orbranched, saturated or unsaturated hydrocarbyl group; provided that ifR¹=H, then R²≠H, Me, or Et. The C₁-C₆ linear or branched, saturated orunsaturated hydrocarbyl group may contain amines or ethers.Alternatively, R¹ and R² may be independently selected from Me, Et, iPr,nPr, tBu, nBu, and secBu.

When X is a halide, exemplary Si-containing film forming compositionsinclude (SiH₃)₂—N—SiH₂Cl, (SiH₃)₂—N—SiH₂Br, or (SiH₃)₂—N—SiH₂I. Thesecompositions may be synthesized according to the reaction:SnX₄+N(SiH₃)₃→N(SiH₃)₂(SiH₂X)+SnX₂⬇+HXI, wherein X is Cl, Br, or I (seeJ. Chem. Soc. Dalton Trans. 1975, p. 1624). Alternatively, dihalosilane[SiH₂X₂, wherein X is Cl, Br, or I] and monohalosilane [SiH₃X, wherein Xis Cl, Br, or I] may be introduced continuously in the gas phase in a1/20 to ¼ ratio and at room temperature with 400 sccm of NH₃ in aflow-through tubular reactor as described by Miller in U.S. Pat. No.8,669,387. The reaction of NH₃ with 2 equivalents of monohalosilaneproduces mostly disilylamine (DSA). DSA then reacts with thedihalosilane to form (SiH₃)₂—N—SiH₂X and HX, wherein X is Cl, Br, or I.One of ordinary skill in the art would recognize that the reaction maytake place in one or two steps (first forming DSA from themonohalosilane and NH₃ and second adding dihalosilane) or in one step(combining the monohalosilane, dichlorosilane, and NH₃ in one step).

When X is an isocyanato group [—NCO], exemplary Si-containing filmforming compositions include (SiH₃)₂—N—SiH₂(NCO). This composition maybe synthesized using dehydrogenerative coupling according to the methoddisclosed by Taniguchi et al. in Angewandte Communications, Angew. Chem.Int. Ed. 2013, 52, 1-5, the teachings of which are incorporated hereinby reference. More particularly, (SiH₃)₃N may be reacted with urea(NH₂CONH₂) to form (SiH₃)₂—N—SiH₂(NCO)+H₂ in the presence of goldnanoparticles supported on alumina.

Wien X is an amino group [—NR¹R²], exemplary Si-containing film formingcompositions include (SiH₃)₂—N—SiH₂(NEt₂), (SiH₃)₂—N—SiH₂(NiPr₂),(SiH₃)₂—N—SiH₂(NHiPr), (SiH₃)₂—N—SiH₂(NHtBu), (SiH₃)₂—N—SiH₂[N(SiH₃)₂],(SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂Cl)], (SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂(NEt₂))],(SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂(NiPr₂))],(SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂(NHtBu))], (SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂OEt)],(SiH₃)₂—N—SiH₂[N(SiH₃)(SiH₂OiPr)], (SiH₃)₂—N—SiH₂[N(SiMe₃)₂],(SiH₃)₂—N—SiH₂[NH(SiMe₃)], (SiH₃)₂—N—SiH₂[N(SiEt₃)₂),(SiH₃)₂—N—SiH₂[N(SiMe₂Et)₂). (SiH₃)₂—N—SiH₂[N(SiMe₂iPr)₂),(SiH₃)₂—N—SiH₂[N(tBu)(SiH₃)), (SiH₃)₂—N—SiH₂[N(SiMe₂nPr)₂),(SiH₃)₂N—SiH₂ NEtMe, (SiH₃)₂N—SiH₂ NMe₂, (SiH₃)₂N—SiH₂ NMeiPr. or(SiH₃)₂N—SiH₂ NEtiPr.

The amino-substituted Si-containing film forming compositions may besynthesized similarly to the halo-substituted Si-containing film formingcompositions disclosed above. More particularly, 200 sccm ofmonohalosilane and 50 sccm of dihalosilane may be introducedcontinuously in the gas phase and at room temperature with 400 sccm ofNH₃ in a flow-through tubular reactor as described in U.S. Pat. No.8,669,387, forming a stream consisting of various silylamines andammonium halide, from which (SiH₃)₂—N—SiH₂[N(SiH₃)₂] may be isolated bymethods easily derived by a person having ordinary skill in the art,such as a method of fractional distillation.

More particularly, (SiH₃)₂—N—SiH₂[N(SiMe₃)₂] may be synthesized from thereaction of SiMe₃-NH—SiMe₃ with tBuLi→(Me₃Si)₂NLi, and reaction of(Me₃Si)₂NLi with (SiH₃)₂—N—SiH₂—Cl→(SiH₃)₂—N—SiH₂—N(SiMe₃)₂+LiCl).

Similarly, (SiH₃)₂—N—SiH₂—NH(SiMe₃) may be synthesized from the reactionof SiMe₃-NH—SiMe₃+(SiH₃)₂—N—SiH₂—Cl→(SiH₃)₂—N—SiH₂—NH—SiMe₃+Me₃SiCl.

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) may be synthesized from the reaction of(SiH₃)₂—N—SiH₂—N(SiH₃)₂ with SnX₃, wherein X is Cl, Br, or I (see J.Chem. Soc. Dalton Trans. 1975, p. 1624). Further substitution of(SiH₃)₂—N—SiH₂—N(SiH₃)₂ may be achieved by increasing the reaction timeand/or adjusting the stoichiometry.

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NEt₂)) may be synthesized from the reactionof (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) and HNEt₂. Further substitution of(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NEt₂)) may be achieved by increasing thereaction time and/or adjusting the stoichiometry.

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NiPr₂)) may be synthesized from the reactionof (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) and HNiPr₂. Further substitution of(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NiPr₂)) may be achieved by increasing thereaction time and/or adjusting the stoichiometry.

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHtBu)) may be synthesized from the reactionof (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) and H₂NtBu. Please note that a similarreaction using H₂NEt may produce low yields of(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(NHEt)).

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(OEt)) may be synthesized from the reactionof (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) and Ethanol (EtOH) in the presence of aHCl scavenger, like NEt₃ or pyridine.

(SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂(OiPr)) may be synthesized from the reactionof (SiH₃)₂—N—SiH₂—N(SiH₃)(SiH₂X) and isopropanol (iPrOH) in the presenceof a HCl scavenger, like NEt₃ or pyridine.

When X is a N-containing C₄-C₁₀ saturated or unsaturated heterocycle,exemplary Si-containing film forming compositions include(SiH₃)₂—N—SiH₂-pyrrolidine, (SiH₃)₂—N—SiH₂-pyrrole, or(SiH₃)₂—N—SiH₂-piperidine. Alternatively, the N-containing C₄-C₁₀saturated or unsaturated heterocycle may also contain hetero-elements,such as P, B, As, Ge, and/or Si.

When X is an alkoxy group, exemplary Si-containing film formingcompositions include (SiH₃)₂—N—SiH₂(OEt). (SiH₃)₂—N—SiH₂(OiPr),(SiH₃)₂N—SiH₂—OSiMe₃, (SiH₃)₂—N—SiH₂—OSiMe₂₀Et, or(SiH₃)₂—N—SiH₂—OSiHMe₂.

N(SiH₃)₂(SiH₂OEt) may also be synthesized from (SiH₃)₂—N—SiH₂Cl and EtOHin the presence of an acid scavenger, such as Et₃N or pyridine.

N(SiH₃)₃+EtOH→N(SiH₃)₂(SiH₂OEt).

Preferably, the disclosed Si-containing film forming compositions havesuitable properties for vapor depositions methods, such as high vaporpressure, low melting point (preferably being in liquid form at roomtemperature), low sublimation point, and/or high thermal stability.

To ensure process reliability, the disclosed Si-containing film formingcompositions may be purified by continuous or fractional batchdistillation prior to use to a purity ranging from approximately 95% w/wto approximately 100% w/w, preferably ranging from approximately 98% w/wto approximately 100% w/w. One of ordinary skill in the art willrecognize that the purity may be determined by H NMR or gas or liquidchromatography with mass spectrometry. The Si-containing film formingcomposition may contain any of the following impurities: halides (X₂),trisilylamine, monohalotrisilylamine, dihalotrisilylamine, SiH₄, SiH₃X,SnX₂, SnX₄, HX, NH₃, NH₃X, monochlorosilane, dichlorosilane, alcohol,alkylamines, dialkylamines, alkylimines, THF, ether, pentane,cyclohexane, heptanes, or toluene, wherein X is Cl, Br, or I.Preferably, the total quantity of these impurities is below 0.1% w/w.The purified composition may be produced by recrystallisation,sublimation, distillation, and/or passing the gas or liquid through asuitable adsorbent, such as a 4A molecular sieve or a carbon-basedadsorbent (e.g., activated carbon).

The concentration of each solvent (such as THF, ether, pentane,cyclohexane, heptanes, and/or toluene), in the purified mono-substitutedTSA precursor composition may range from approximately 0% w/w toapproximately 5% w/w, preferably from approximately 0% w/w toapproximately 0.1% w/w. Solvents may be used in the precursorcomposition's synthesis. Separation of the solvents from the precursorcomposition may be difficult if both have similar boiling points.Cooling the mixture may produce solid precursor in liquid solvent, whichmay be separated by filtration. Vacuum distillation may also be used,provided the precursor composition is not heated above approximately itsdecomposition point.

The disclosed Si-containing film forming composition contains less than5% v/v, preferably less than 1% v/v, more preferably less than 0.1% v/v,and even more preferably less than 0.01% v/v of any of its mono-, dual-or tris-, analogs or other reaction products. This embodiment mayprovide better process repeatability. This embodiment may be produced bydistillation of the Si-containing film forming composition.

Purification of the disclosed Si—Containing film forming composition mayalso produce concentrations of trace metals and metalloids ranging fromapproximately 0 ppbw to approximately 500 ppbw, and more preferably fromapproximately 0 ppbw to approximately 100 ppbw. These metal or metalloidimpurities include, but are not limited to, Aluminum (Al), Arsenic (As),Barium (Ba), Beryllium (Be), Bismuth (Bi), Cadmium (Cd), Calcium (Ca),Chromium (Cr), Cobalt (Co), Copper (Cu), Gallium (Ga), Germanium (Ge),Hafnium (Hf), Zirconium (Zr), Indium (ln), Iron (Fe), Lead (Pb), Lithium(Li), Magnesium (Mg), Manganese (Mn), Tungsten (W), Nickel (Ni),Potassium (K), Sodium (Na), Strontium (Sr), Thorium (Th), Tin (Sn),Titanium (Ti), Uranium (U), Vanadium (V) and Zinc (Zn). Theconcentration of X (where X=Cl, Br, I) in the purified mono-substitutedTSA precursor composition may range between approximately 0 ppmw andapproximately 100 ppmw and more preferably between approximately 0 ppmwto approximately 10 ppmw.

The disclosed Si-containing film forming compositions may be suitablefor the deposition of Si-containing films by various ALD or CVDprocesses and may have the following advantages:

-   -   liquid at room temperature or having a melting point lower than        50° C.;    -   thermally stable to enable proper distribution (gas phase or        direct liquid injection) without particles generation; and/or    -   suitable reactivity with the substrate to permit a wide        self-limited ALD window, allowing deposition of a variety of        Si-containing films.

Silicon nitride and silicon oxide containing films (referred to asSiO_(x)N_(y)) may be deposited by CVD or ALD using one or a combinationof reactants selected from the group comprising of N₂, H₂, NH₃, O₂, H₂O,H₂O₂, O₃, NO, NO₂, N₂O, a carboxylic acid, an alcohol, a diol,hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic amines (such asNMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃, (SiMe₃)₂NH), pyrazoline,pyridine, diamines (such as ethylene diamine), a combination thereof,and the plasma product thereof.

Ternary or quaternary films may be deposited using the Si-containingfilm forming compositions with one or several other precursorscontaining elements selected from As, B, P, Ga, Ge, Sn, Sb, Al, In, or atransition metal precursor, and possibly one or more reactant listedabove. Typical precursors that may be used along with the disclosedSi-containing film forming compositions are selected from the familiesof:

-   -   Metal Halides (for example, TiCl₄, TiI₄, TaCl₅, HfCl₄, ZrCl₄,        AlCl₃, NbF₅, etc.);    -   Alkyls (Al, Ge, Ga, In, Sb, Sn, Zn), such as trimethylaluminum,        diethylzinc, triethylgalium;    -   Hydrides (GeH₄, alanes, etc.);    -   Alkylamides (metals of group IV and V transition metals);    -   Imido group (metals of group V and VI);    -   Alkoxides (metals of group IV. V);    -   Cyclopentadienyls (Ru, Co, Fe, Group IV transition metals,        lanthanides etc.);    -   Carbonyls (ex: Ru, Co, Fe, Ni);    -   Amidinates and guanidinates (ex: Co, Mn, Ni, Cu, Sc, etc.);    -   Beta-diketonates (ex: Sc, Cu, lanthanides);    -   Beta-diketoimines (Cu, Ni, Co, etc;    -   Bis-trialkylsilylamides (Ni, Co, Fe, etc.);    -   Oxo groups (RuO₄, WOCl₄, PO(OEt)₃, AsO(OEt)₃, etc.);    -   Or heteroleptic molecules having a combination of the above        ligands.

The disclosed Si-containing film forming compositions may also be usedin conjunction with another silicon source, such as a halosilane(possibly selected from SiH₃Cl, SiH₂Cl₂, SiHCl₃, SiCl₄, SiBr₄, SiI₄,SiHI₃, SiH₂I₂, SiH₃I, SiF₄), a polysilane SiH_(x)H_(2x+2), or a cyclicpolysilane SiH_(x)H_(2x), a halo-polysilane (Si_(x)Cl_(2x+2),Si_(x)H_(y)Cl_(2x+2−y), such as HCDS, OCTS, PCDS, MCDS or DCDS, acarbosilane having a Si—(CH₂)_(n)—Si backbone, with n=1 or 2.

Also disclosed are methods of using the disclosed Si-containing filmforming compositions for vapor deposition methods, including various CVDand ALD methods. The disclosed methods provide for the use of thedisclosed Si-containing film forming compositions for deposition ofsilicon-containing films, preferably silicon nitride (SiN) films,silicon-oxide (SiO) films, and nitrogen doped silicon-oxide films. Thedisclosed methods may be useful in the manufacture of semiconductor,photovoltaic, LCD-TFT, flat panel type devices, refractory materials, oraeronautics.

The disclosed methods for forming a silicon-containing layer on asubstrate include: placing a substrate in a reactor, delivering into thereactor a vapor including the Si-containing film forming composition,and contacting the vapor with the substrate (and typically directing thevapor to the substrate) to form a silicon-containing layer on thesurface of the substrate. Alternatively, the substrate is moved to thechamber that contains the precursor vapors (spatial ALD) and then movedto another area that contains the reactant.

Other physical treatment steps may be carried in between the exposure toprecursor and reactants, such as a flash anneal, a UV cure, etc.

The methods may include forming a bimetal-containing layer on asubstrate using the vapor deposition process and, more specifically, fordeposition of SiMO_(x) films wherein x is 4 and M is Ti, Hf, Zr, Ta, Nb,V, Al, Sr, Y, Ba, Ca, As, B, P, Sb, Bi, Sn, lanthanides (such as Er), orcombinations thereof. The disclosed methods may be useful in themanufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel typedevices. An oxygen source, such as O₃, O₂, H₂O, NO, H₂O₂, acetic acid,formalin, para-formaldehyde, alcohol, a diol, oxygen radicals thereof,and combinations thereof, but preferably O₃ or plasma treated O₂, mayalso be introduced into the reactor.

The disclosed Si-containing film forming compositions may be used todeposit silicon-containing films using any deposition methods known tothose of skill in the art. Examples of suitable deposition methodsinclude chemical vapor deposition (CVD) or atomic layer deposition(ALD). Exemplary CVD methods include thermal CVD, pulsed CVD (PCVD), lowpressure CVD (LPCVD), sub-atmospheric CVD (SACVD) or atmosphericpressure CVD (APCVD), hot-wire CVD (HWCVD, also known as cat-CVD, inwhich a hot wire serves as an energy source for the deposition process),radicals incorporated CVD, plasma enhanced CVD (PECVD) including but notlimited to flowable CVD (FCVD), and combinations thereof. Exemplary ALDmethods include thermal ALD, plasma enhanced ALD (PEALD), spatialisolation ALD, hot-wire ALD (HWALD), radicals incorporated ALD, andcombinations thereof. Super critical fluid deposition may also be used.The deposition method is preferably FCVD, ALD, PE-ALD, or spatial ALD inorder to provide suitable step coverage and film thickness control.

The Si-containing film forming compositions are delivered into a reactorin vapor form by conventional means, such as tubing and/or flow meters.The vapor form of the compositions may be produced by vaporizing theneat or blended composition solution through a conventional vaporizationstep such as direct vaporization, distillation, by bubbling. Thecomposition may be fed in liquid state to a vaporizer where it isvaporized before it is introduced into the reactor. Prior tovaporization, the composition may optionally be mixed with one or moresolvents. The solvents may be selected from the group consisting oftoluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane,hexane, pentane, or others. The resulting concentration may range fromapproximately 0.05 M to approximately 2 M.

Alternatively, the Si-containing film forming compositions may bevaporized by passing a carrier gas into a container containing theprecursor or by bubbling of the carrier gas into the precursor. Thecomposition may optionally be mixed in the container with one or moresolvents. The solvents may be selected from the group consisting oftoluene, ethyl benzene, xylene, mesitylene, decane, dodecane, octane,hexane, pentane, or others. The resulting concentration may range fromapproximately 0.05 M to approximately 2 M. The carrier gas may include,but is not limited to, Ar, He, or N₂, and mixtures thereof. Bubblingwith a carrier gas may also remove any dissolved oxygen present in theneat or blended composition. The carrier gas and composition are thenintroduced into the reactor as a vapor.

If necessary, the container may be heated to a temperature that permitsthe Si-containing film forming composition to be in liquid phase and tohave a sufficient vapor pressure. The container may be maintained attemperatures in the range of, for example, 0 to 150° C. Those skilled inthe art recognize that the temperature of the container may be adjustedin a known manner to control the amount of composition vaporized. Thetemperature is typically adjusted to reach a vapor pressure of 0.1-100torr, preferably around 1-20 torr.

The vapor of the Si-containing film forming composition is generated andthen introduced into a reaction chamber containing a substrate. Thetemperature and the pressure in the reaction chamber and the temperatureof the substrate are held at conditions suitable for vapor deposition ofat least part of the mono-substituted TSA precursor onto the substrate.In other words, after introduction of the vaporized composition into thereaction chamber, conditions within the reaction chamber are adjustedsuch that at least part of the vaporized precursor is deposited onto thesubstrate to form the Si-containing layer. One of ordinary skill in theart will recognize that “at least part of the vaporized compound isdeposited” means that some or all of the compound reacts with or adheresto the substrate. Herein, a reactant may also be used to help information of the Si-containing layer. Furthermore, the Si-containinglayer may be cured by UV and Electron beam.

The reaction chamber may be any enclosure or chamber of a device inwhich deposition methods take place, such as, without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other suchtypes of deposition systems. All of these exemplary reaction chambersare capable of serving as an ALD or CVD reaction chamber. The reactionchamber may be maintained at a pressure ranging from about 0.5 mTorr toabout 20 Torr for all ALD and subatmospheric CVD. Subatmospheric CVD andatmospheric CVD pressures may range up to 760 Torr (atmosphere). Inaddition, the temperature within the reaction chamber may range fromabout 0° C. to about 800° C. One of ordinary skill in the art willrecognize that the temperature may be optimized through mereexperimentation to achieve the desired result.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder or controlling the temperatureof the reactor wall. Devices used to heat the substrate are known in theart. The reactor wall is heated to a sufficient temperature to obtainthe desired film at a sufficient growth rate and with desired physicalstate and composition. A non-limiting exemplary temperature range towhich the reactor wall may be kept from approximately 20° C. toapproximately 800° C. When a plasma deposition process is utilized, thedeposition temperature may range from approximately 0° C. toapproximately 550° C. Alternatively, when a thermal process isperformed, the deposition temperature may range from approximately 200°C. to approximately 800° C.

Alternatively, the substrate may be heated to a sufficient temperatureto obtain the desired silicon-containing film at a sufficient growthrate and with desired physical state and composition. A non-limitingexemplary temperature range to which the substrate may be heatedincludes from 50° C. to 600° C. Preferably, the temperature of thesubstrate remains less than or equal to 500° C.

Alternatively, the ALD process may be carried at a substrate temperaturebeing set below a self-decomposition of the precursor. One of ordinaryskill in the art would recognize how to determine the self-decompositiontemperature of the precursor.

The reactor contains one or more substrates onto which the films will bedeposited. A substrate is generally defined as the material on which aprocess is conducted. The substrates may be any suitable substrate usedin semiconductor, photovoltaic, flat panel, or LCD-TFT devicemanufacturing. Examples of suitable substrates include wafers, such assilicon, silica, glass, plastic or GaAs wafers. The wafer may have oneor more layers of differing materials deposited on it from a previousmanufacturing step. For example, the wafers may include silicon layers(crystalline, amorphous, porous, etc.), silicon oxide layers, siliconnitride layers, silicon oxy nitride layers, carbon doped silicon oxide(SiCOH) layers, photoresist layers, anti-reflective layers, orcombinations thereof. Additionally, the wafers may include copper layersor noble metal layers (e.g. platinum, palladium, rhodium, or gold). Thelayers may include oxides which are used as dielectric materials in MIM,DRAM, STT RAM, PC-RAM or FeRam technologies (e.g., ZrO₂ based materials,HfO₂ based materials, TiO₂ based materials, rare earth oxide basedmaterials, ternary oxide based materials such as strontium rutheniumoxide (SRO), etc.) or from nitride-based films (e.g., TaN) that are usedas an oxygen barrier between copper and the low-k layer. The wafers mayinclude barrier layers, such as manganese, manganese oxide, etc. Plasticlayers, such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)(PEDOT:PSS) may also be used. The layers may be planar or patterned. Forexample, the layer may be a patterned photoresist film made ofhydrogenated carbon, for example CH_(x), wherein x is greater than zero.The disclosed processes may deposit the silicon-containing layerdirectly on the wafer or directly on one or more than one (whenpatterned layers form the substrate) of the layers on top of the wafer.Furthermore, one of ordinary skill in the art will recognize that theterms “film” or “layer” used herein refer to a thickness of somematerial laid on or spread over a surface and that the surface may be atrench or a line. Throughout the specification and claims, the wafer andany associated layers thereon are referred to as substrates. In manyinstances though, the preferred substrate utilized may be selected fromcopper, silicon oxide, photoresist, hydrogenated carbon, TiN, SRO, Ru,and Si type substrates, such as polysilicon or crystalline siliconsubstrates. For example, a silicon nitride film may be deposited onto aSi layer. In subsequent processing, alternating silicon oxide andsilicon nitride layers may be deposited on the silicon nitride layerforming a stack of multiple SiO₂/SiN layers used in 3D NAND gates.Furthermore, the substrate may be coated with patterned or unpatternedorganic or inorganic films.

In addition to the disclosed Si-containing film forming compositions, areactant may also be introduced into the reactor. The reactant may be anoxidizing agent, such as one of O₂, O₃, H₂O, H₂O₂; oxygen containingradicals, such as O or OH, NO, NO₂; carboxylic acids such as formicacid, acetic acid, propionic acid, radical species of NO, NO₂, or thecarboxylic acids; para-formaldehyde; and mixtures thereof. Preferably,the oxidizing agent is selected from the group consisting of O₂. O₃.H₂O, H₂O₂, oxygen containing radicals thereof such as O or OH, andmixtures thereof. Preferably, when an ALD process is performed, thereactant is plasma treated oxygen, ozone, or combinations thereof. Whenan oxidizing agent is used, the resulting silicon containing film willalso contain oxygen.

Alternatively, the reactant may be a nitrogen-containing reactant, suchas one of N₂, NH₃, hydrazines (for example, N₂H₄, MeHNNH₂, MeHNNHMe),organic amines (for example, N(CH₃)H₂, N(C₂H₅)H₂, N(CH₃)₂H, N(C₂H₅)₂H,N(CH₃)₃, N(C₂H₅)₃, (SiMe₃)₂NH), pyrazoline, pyridine, diamine (such asethylene diamine), radicals thereof, or mixtures thereof. When anN-containing source agent is used, the resulting silicon containing filmwill also contain nitrogen.

When a reducing agent is used, such as H₂, H radicals, but also otherH-containing gases and precursors such as metal and metalloid hydrides,the resulting silicon containing film may be pure Si.

In summary, the reactant is selected from the group consisting of O₂,O₃, H₂O, H₂O₂, NO, NO₂, N₂O, alcohols, diols, carboxylic adds, ketones,ethers, O atoms, O radicals, O ions, ammonia, N₂, N atoms, N radicals, Nions, saturated or unsaturated hydrazine, amines, diamines,ethanolamine, H₂, H atoms, H radicals, H ions, and combinations thereof.

The reactant may be treated by plasma, in order to decompose thereactant into its radical form. N₂ may also be utilized when treatedwith plasma. For instance, the plasma may be generated with a powerranging from about 50 W to about 2000 W, preferably from about 100 W toabout 500 W. The plasma may be generated or present within the reactoritself. Alternatively, the plasma may generally be at a location removedfrom the reactor, for instance, in a remotely located plasma system. Oneof skill in the art will recognize methods and apparatus suitable forsuch plasma treatment.

The Si-containing film forming compositions may also be used with ahalosilane or polyhalodisilane, such as hexachlorodisilane,pentachlorodisilane, or tetrachlorodisilane, and one or more reactantsto form Si, SiCN, or SiCOH films. PCT Publication Number WO2011/123792discloses a SiN layer (not a Si or SiCOH layer), and the entire contentsof which are incorporated herein in their entireties.

When the desired silicon-containing film also contains another element,such as, for example and without limitation, Ti, Hf, Zr, Ta, Nb, V, Al,Sr, Y, Ba, Ca, As, B, P, Sb, Bi, Sn, Ge lanthanides (such as Er), orcombinations thereof, another precursor may include a metal-containingprecursor which is selected from, but not limited to:

-   -   Metal Halides (e.g., TiCl₄, TiI₄, TaCl⁵, HfCl₄, ZrCl₄, AlCl₃,        NbF₅, etc);    -   Alkyls (Al, Ge, Ga, In, Sb, Sn, Zn), such as trimethylaluminum,        diethylzinc, triethylgalium;    -   Hydrides (GeH4, alanes, etc.);    -   Alkylamides (metals of group IV and V transition metals);    -   Imido group (metals of group V and VI);    -   Alkoxides (metals of group IV, V);    -   Cyclopentadienyls (Ru, Co, Fe, Group IV transition metals,        lanthanides, etc);    -   Carbonyls (ex: Ru, Co, Fe, Ni);    -   Amidinates and guanidinates (ex: Co, Mn, Ni, Cu, Sc, etc.;    -   Beta-diketonates (e.g.: Sc, Cu, lanthanides);    -   Beta-diketoimines (Cu, Ni, Co, etc.);    -   Bis-trialkylsilylamides (Ni, Co, Fe, etc);    -   Oxo groups (RuO₄, WOCl₄, PO(OEt)₃, AsO(OEt)₃, etc);    -   Heteroleptic molecules having a mixed set of ligands selected        from the above families.

The Si-containing film forming compositions and one or more reactantsmay be introduced into the reaction chamber simultaneously (e.g., CVD),sequentially (e.g., ALD), or in other combinations. For example, theSi-containing film forming composition may be introduced in one pulseand two additional metal sources may be introduced together in aseparate pulse (e.g., modified ALD). Alternatively, the reaction chambermay already contain the reactant prior to introduction of theSi-containing film forming composition. The reactant may be passedthrough a plasma system localized or remotely from the reaction chamber,and decomposed to radicals. Alternatively, the Si-containing filmforming composition may be introduced to the reaction chambercontinuously while other metal sources are introduced by pulse (e.g.,pulsed-CVD). In each example, a pulse may be followed by a purge orevacuation step to remove excess amounts of the component introduced. Ineach example, the pulse may last for a time period ranging from about0.01 s to about 20 s, alternatively from about 0.3 s to about 3 s,alternatively from about 0.5 s to about 2 s. In another alternative, theSi-containing film forming composition and one or more reactants may besimultaneously sprayed from a shower head under which a susceptorholding several wafers is spun (e.g., spatial ALD).

In a non-limiting exemplary ALD type process, the vapor phase of theSi-containing film forming composition is introduced into the reactionchamber, where it is contacted with a suitable substrate and forms asilicon-containing layer on the substrate. Excess composition may thenbe removed from the reaction chamber by purging and/or evacuating thereaction chamber. An oxygen source is introduced into the reactionchamber where it reacts with the silicon-containing layer in aself-limiting manner. Any excess oxygen source is removed from thereaction chamber by purging and/or evacuating the reaction chamber. Ifthe desired film is a silicon oxide film, this two-step process mayprovide the desired film thickness or may be repeated until a filmhaving the necessary thickness has been obtained.

Alternatively, if the desired film is a silicon metal oxide film (i.e.,SiMO_(x), wherein x may be 4 and M is Ti, Hf, Zr, Ta, Nb, V, Al, Sr, Y,Ba, Ca, As, B, P, Sb, Bi, Sn, Ge, lanthanides (such as Er), orcombinations thereof), the two-step process above may be followed byintroduction of a second vapor of a metal-containing precursor into thereaction chamber. The metal-containing precursor will be selected basedon the nature of the silicon metal oxide film being deposited. Afterintroduction into the reaction chamber, the metal-containing precursoris contacted with the silicon oxide layer on the substrate. Any excessmetal-containing precursor is removed from the reaction chamber bypurging and/or evacuating the reaction chamber. Once again, an oxygensource may be introduced into the reaction chamber to react with themetal-containing precursor. Excess oxygen source is removed from thereaction chamber by purging and/or evacuating the reaction chamber. If adesired film thickness has been achieved, the process may be terminated.However, if a thicker film is desired, the entire four-step process maybe repeated. By alternating the provision of the Si-containing filmforming compositions, metal-containing precursor, and oxygen source, afilm of desired composition and thickness may be deposited.

Additionally, by varying the number of pulses, films having a desiredstoichiometric M:Si ratio may be obtained. For example, a SiMO₂ film maybe obtained by having one pulse of the mono-substituted TSA precursorand one pulses of the metal-containing precursor, with each pulse beingfollowed by pulses of the oxygen source. However, one of ordinary skillin the art will recognize that the number of pulses required to obtainthe desired film may not be identical to the stoichiometric ratio of theresulting film.

In a non-limiting exemplary PE-ALD type process, the vapor phase of theSi-containing film forming composition is introduced into the reactionchamber, where it is contacted with a suitable substrate, while a lowreactivity oxygen source, such as O₂, is continuously flowing to thechamber. Excess composition may then be removed from the reactionchamber by purging and/or evacuating the reaction chamber. A plasma isthen lit to activate the oxygen source to react with the absorbedmono-substituted TSA precursor in a self-limiting manner. The plasma isthen switched off and the flow of the Si-containing film formingcomposition may proceed immediately after. This two-step process mayprovide the desired film thickness or may be repeated until a siliconoxide film having the necessary thickness has been obtained. The siliconoxide film may contain some C impurities, typically between 0.005% and2%. The oxygen gas source and the substrate temperature may be selectedby one of ordinary skill in the art so as to prevent reaction betweenthe oxygen source and the mono-substituted TSA when the plasma is off.

Dialkylamino-substituted TSA are particularly suitable for such aprocess, and are preferably (SiH₃)₂N—SiH₂—NEt₂, (SiH₃)₂N—SiH₂—NiPr₂ or(SiH₃)₂N—SiH₂—NHR, R being -tBu or —SiMe₃.

In another non-limiting exemplary PE-ALD type process, the vapor phaseof the Si-containing film forming compositions is introduced into thereaction chamber, where it is contacted with a suitable substrate, whilea low reactivity nitrogen source, such as N₂, is continuously flowing tothe chamber. Excess composition may then be removed from the reactionchamber by purging and/or evacuating the reaction chamber. A plasma isthen lit to activate the nitrogen source to react with the absorbedmono-substituted TSA precursor in a self-limiting manner. The plasma isthen switched off and flow of the Si-containing film forming compositionmay proceed immediately after. This two-step process may provide thedesired film thickness or may be repeated until a silicon nitride filmhaving the necessary thickness has been obtained. The silicon nitridefilm may contain some C impurities, typically between 0.5% and 10%. Thenitrogen gas source and the substrate temperature may be selected by oneof ordinary skill in the art so as to prevent reaction between thenitrogen source and the mono-substituted TSA when the plasma is off.Amino-substituted TSA and mono-halo TSA are particularly suitable forsuch a process, and are preferably (SiH₃)₂N—SiH₂—Cl, (SiH₃)₂N—SiH₂—NEt₂,(SiH₃)N—SiH₂—NiPr₂, (SiH₃)₂N—SiH₂—NHR, R being -tBu or —SiMe₃, or(SiH₃)₂N—SiH₂—N(SiH₃)₂.

In a non-limiting exemplary LPCVD type process, the vapor phase of theSi-containing film forming compositions, preferably containing amono-halo substituted TSA precursor, is introduced into the reactionchamber holding the substrates and kept at a pressure typically between0.1 and 10 torr, and more preferably between 0.3 and 3 torr, and at atemperature between 250° C. and 800° C., preferably between 350° C. and600° C., where it is mixed with a reactant, typically NH₃. A thinconformal SiN film may thus be deposited on the substrate(s). One ofordinary skill in the art will recognize that the Si/N ratio in the filmmay be tuned by adjusting the mono-substituted TSA precursor andN-source flow rates.

In another alternative, dense SiN films may be deposited using an ALDmethod with hexachlorodisilane (HCDS), pentachlorodisilane (PCDS),monochlorodisilane (MCDS), dichlorodisilane (DCDS) or monochlorosilane(MCS), the disclosed Si-containing film forming compositions, and anammonia reactant. The reaction chamber may be controlled at 5 Torr, 550°C., with a 55 sccm continuous flow of Ar. An approximately 10 secondlong pulse of the disclosed Si-containing film forming composition at aflow rate of approximately 1 sccm is introduced into the reactionchamber. The composition is purged from the reaction chamber with anapproximately 55 sccm flow of Ar for approximately 30 seconds. Anapproximately 10 second pulse of HCDS at a flow rate of approximately 1sccm is introduced into the reaction chamber. The HCDS is purged fromthe reaction chamber with an approximately 55 sccm flow of Ar forapproximately 30 seconds. An approximately 10 second long pulse of NH₃at a flow rate of approximately 50 sccm is introduced into the reactionchamber. The NH₃ is purged from the reaction chamber with anapproximately 55 sccm flow of Ar for approximately 10 seconds. These 6steps are repeated until the deposited layer achieves a suitablethickness. One of ordinary skill in the art will recognize that theintroductory pulses may be simultaneous when using a spatial ALD device.As described in PCT Pub No WO2011/123792, the order of the introductionof the precursors may be varied and the deposition may be performed withor without the NH₃ reactant in order to tune the amounts of carbon andnitrogen in the SiCN film. One of ordinary skill in the art wouldfurther recognize that the flow rates and pulse times may vary amongstdifferent deposition chambers and would be able to determine thenecessary parameter for each device.

In a non-limiting exemplary process, the vapor phase of the disclosedSi-containing film forming compositions, preferably containing mono-halosubstituted TSA, is introduced into the reaction chamber holding asubstrate having a porous low-k film. A pore sealing film may bedeposited in the conditions described in US 2015/0004806 (i.e., byintroducing the disclosed silicon-containing film forming composition,an oxidant (such as ozone, hydrogen peroxide, oxygen, water, methanol,ethanol, isopropanol, nitric oxide, nitrous dioxide, nitrous oxide,carbon monoxide, or carbon dioxide), and a halogen free catalystcompound (such as nitric acid, phosphoric acid, sulfuric acid,ethylenediaminetetraacetic acid, picric acid, or acetic acid) to areaction chamber and exposing the substrate to the process gases underconditions such that a condensed flowable film forms on the substrate).

In yet another alternative, a silicon-containing film may be depositedby the flowable PECVD method disclosed in U.S. Patent ApplicationPublication No. 2014/0051264 using the disclosed compositions and aradical nitrogen- or oxygen-containing reactant. The radical nitrogen-or oxygen-containing reactant, such as NH₃ or H₂O respectively, isgenerated in a remote plasma system. The radical reactant and the vaporphase of the disclosed precursors are introduced into the reactionchamber where they react and deposit the initially flowable film on thesubstrate. Applicants believe that the nitrogen atoms of the(SiH₃)₂N—(SiH₂—X) structure helps to further improve the flowability ofthe deposited film, resulting in films having less voids, especiallywhen X is an amino group, and more specifically when X is a disilylaminogroup like —N(SiH₃)₂.

The silicon-containing films resulting from the processes discussedabove may include SiO₂, nitrogen doped silicon oxide, SiN, SiON, SiCN,SiCOH, or MSiN_(y)O_(x), wherein M is an element such as Ti, Hf, Zr, Ta.Nb, V, Al, Sr, Y, Ba, Ca. As, B, P, Sb, Bi, Sn, Ge. and x, y may be from0-4 and y+x=4, depending of course on the oxidation state of M. One ofordinary skill in the art will recognize that by judicial selection ofthe appropriate mono-substituted TSA precursor and reactants, thedesired film composition may be obtained.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, thesilicon-containing film may be exposed to a temperature ranging fromapproximately 200° C. and approximately 1000° C. for a time ranging fromapproximately 0.1 second to approximately 7200 seconds under an inertatmosphere, a H-containing atmosphere, a N-containing atmosphere, anO-containing atmosphere, or combinations thereof. Most preferably, thetemperature is 600° C. for less than 3600 seconds under a reactiveH-containing atmosphere. The resulting film may contain fewer impuritiesand therefore may have improved performance characteristics. Theannealing step may be performed in the same reaction chamber in whichthe deposition process is performed. When the deposition process is aFCVD, the curing step is preferably an oxygen curing step, carried outat a temperature lower than 600° C. The oxygen containing atmosphere maycontain H₂O or O₃. Alternatively, the substrate may be removed from thereaction chamber, with the annealing/flash annealing process beingperformed in a separate apparatus.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

The examples described herein are TSA based precursors, i.e.,halosilazane and mono-substituted TSA.

Experimental Procedure

Reaction mixtures, starting materials, solvents and products may beanalyzed by any suitable means, such as by gas chromatography using partof the stream or aliquots. Gas Chromatographic analysis performed on Gaschromatographs (Agilent Technologies 7890A GC system equipped withthermal conductivity detector and mass spectrometer Agilent Technologies5975C VL MSD system with triple axis detector and Agilent Technologies6890N Network GC system equipped with thermal conductivity detector andmass spectrometer Agilent 5973 Network mass selective detector) equippedwith Thermal Conductivity Detector (TCD). An injection port is underinert (N₂, Ar) atmosphere. Exemplary method: Column: Rtx-1 (Cross bondDimethyl Polysiloxane) 105 m×0.53 mm×5 μm. Detector T=250° C.; Referenceflow: 20 mL/min; Makeup flow: 5 mL/min; Carrier gas: 5 mL/min (Helium);Oven: 35° C., 8 min, ramp 20° C./min, 200° C., 13 min; Injector: 200°C.; Splitless mode; Sample Size: 1.0 μL.

Raman spectroscopy were measured on a Kaiser RamanRxn2™ Multi-channelRaman Analyzer equipped with the non-contact probe and immersion probes.All measurements were performed for samples in the closed flask orquartz cell without any contact with the atmosphere.

Reagents: TSA (purity 99.8%, relative amount of TSA-Cl 0.09% w/w, ALAM),Diisopropylaminotrisilylamine (purity 99.1% w./w., ALAM),Hexachloroethane (99%, Sigma-Aldrich), Ph₃CCl (trityl chloride)(purity≥97.0%, Sigma-Aldrich), Bromotriphenylmethane (purity≥98.0%,Sigma-Aldrich) and BPh₃ (purity≥97.0%, Sigma-Aldrich, contains <2% H₂O)used as received. Ru/C (Johnson Matthey or Sigma-Aldrich GreenAlternative, extent of labeling: 5 wt % loading, matrix activated carbonsupport), Pd/C, and Pt/C (Sigma-Aldrich Green Alternative, extent oflabeling: 10 wt % loading, matrix activated carbon support) heated at300° C. for 48 hours under vacuum to remove oxygen and moisture. Toluene(anhydrous, 99.8%, Sigma-Aldrich) used as received and operated only inglove box under nitrogen atmosphere with less than 0.5 ppm of O₂ andwater.

The relative selectivity of halogenation process is expressed as aselectivity coefficient (r) from GC chromatogram, wherein:r(%)=I _(TSA-Cl)/(I _(TSA-Cl) +ΣI _((all side products))),where I_(TSA-Cl) is the intensity of TSA-Cl signal in GC chromatogram ofproducts, ΣI_((all side products)) is sum of the intensities of all sideproducts, which may include SiH₄, MCS, DCS, (H₃Si)₂N(SiHCl₂),(H₃Si)N(SiH₂Cl)₂, (H₃Si)N(SiH₂)N(SiH₃)₃, other chlorinated andnon-chlorinated TSA oligomers.

The following comparative examples illustrate that the common approachesfor halogenation of silanes are not applicable for halogenation ofsilazanes. Table 2 is a summary of the tests of the conventionalapproaches to halogenate TSA illustrated from Comparative Example 1 to6.

Comparative Example 1: TSA Bromination with SnBr₄

A mixture of 16.7 g (156 mmol) TSA in 10 ml Dodecane was prepared in a300 cc glass flask. To the flask, a solution of 42.4 g (97 mmol) ofSnBr₄ in 14.4 ml Dodecane was added dropwise while keeping thetemperature between −7 and 3° C. The reaction mix turned milky whiteupon starting the addition. The volatiles from the reaction mix werecollected in two consecutive (dry ice cooled and liquid N₂ cooled)traps. The content of the dry ice trap was a suspension of white solids,which continuously formed after filtration attempts. The GC analysisshowed presence of 4.3% TSA-Br, 1.7% TSA-Br₂, 19.8% BDSASi, 13.8%Bromosilane. The estimated TSA-Br yield is 5.9%.

Comparative Example 2: TSA Chlorination with PCl₃

Inside a glove box, a 10 cc high pressure glass tube was charged with0.35 g (2.5 mmol) PCl₃. The tube was connected to manifold and 0.92 g(8.6 mmol) TSA were cryotrapped into it. The content was warmed up toroom temperature and stirred for 4 hrs. Yellow solid was formed and thepressure inside went up from 0 to 5 psig. Top of the tube was cooleddown with dry ice and the volatiles were removed down to 65 T at −4° C.Only traces of TSA-Cl were detected in the residue by GC.

Comparative Example 3: TSA Chlorination with Ph₂PCl

Experiment similar to Comparative example 2 was repeated with 1.01 g(4.6 mmol) Ph₂PCl and 0.68 g (6.3 mmol) TSA. Intensive bubbling andsolids formation was observed upon warming the reaction mixture. Afterthe reaction subsided, the volatiles were removed to <1 T at 23° C., inwhich ˜0.4% TSA-Cl (estimated yield 0.2%) were detected by GC. Novolatile products were found in a Toluene extract of the solid reactionresidue.

Comparative Example 4: TSA Chlorination with BCl₃

Experiment similar to #2 was repeated with 0.36 g (3.1 mmol) BCl₃ and0.96 g (8.9 mmol) TSA. Raman spectra did not detect signs of thereaction upon warming the mixture. After stirring the mix at 28° C. for20 min, top of the tube was cooled with dry ice and the volatiles wereremoved down to 55 T at −4° C. and collected in two consecutive traps.The GC analysis of the dry ice trap showed 1% TSA-Cl (estimated yield2.4%).

Comparative Example 5: TSA-Hal Via H/Hal Redistribution

Inside a glove box, three 2 cc vials were charged with TSA/SiBr₄,TSA/SiCl₄ and TSA/SiHCl₃ mixtures (˜4:1 mol ratio) with AlBr₃ or AlCl₃(˜10% mol of the Halosilane amount). The contents were analyzed by GC.No TSA-Hal peaks were detected in the mixtures with SiHal₄. The SiHCl₃containing mixture showed presence of 0.1% TSA-Cl, 1.9% TSA-Cl₂, 9.9%BDSASi and several heavier unidentified peaks.

Comparative Example 6: TSA-Cl from 2.5 Equiv. TSA and 1 Equiv. S₂Cl₂

Inside a glove box, a 20 mL vial was charged with TSA (4.0 g, 37.3 mmol)and S₂Cl₂ (2.0 g, 14.8 mmol). Moderate gas evolution continued for twohours, while some amount of solid formed. The resulted mixture wasfiltered and filtrate was analyzed by GC. GC, 2.5 h after reactionstart: H₃SiSH (3.3%), (H₃Si)₃N (86.3%), (H₃Si)₂N(SiH₂Cl) (8.8%). GC, 20h after reaction start: H₃SiSH (6.6%). (H₃Si)₃N (79.2%),(H₃Si)₂N(SiH₂Cl) (11.9%). (H₃Si)₂N(SiH₂)N(SiH₃)₂ (0.9%).

TABLE 2 Summary of the tests of the conventional approaches tohalogenate TSA Approach/ Yield halogenating of agent TSA-X Notes SnBr₄<10% TSA-X was detected in the products. HCl/ HBr byproduct cleaved Si—Nbond. Adding tertiary amines to the system caused desilylating couplingresulted in formation of polymers and highly volatile pyrophoriccompounds. Halophosphines: <10% Traces TSA-X were detected in theproducts. PCl₃/PBr₃, Ph₂PCl Side-reactions causepolymerization of thereaction mixture with formation of solid reaction product (extremelyfast in case of Ph₂PCl). BCl₃/BBr₃ <10% Traces TSA-X were detected inthe products Side-reactions cause polymerization of the reactionmixture. SiBr₄, SiCl₄, <10% Traces TSA-X were detected in the products.HSiCl₃ Side-reactions cause polymerization of the reaction mixture.S₂Cl₂, Cl₃CSCl <10% Side-reactions cause polymerization of the reactionmixture and Si—S coupling.

While small amount of TSA-Cl was formed in the comparative examples, notall reactions were selective toward TSA-Cl and the yield of TSA-X in theabove comparative examples 1-6 is not exceed 10%. Thus, low selectivityof reactions, formation of gaseous and solid byproducts precludeutilization of these reactions for industrial applications.

Comparative Example 7: Halogenation of TSA with C₂Cl₆ in TSA, Toluene,without and with Catalysts

Pongkittiphan et al. (“Hexachloroethane: a Highly Efficient Reagent forthe Synthesis of Chlorosilanes from Hydrosilanes”; V. Pongkittiphan, E.A. Theodorakis, W. Chavasiri; Tetrahedron Letters, v.50 (2009), p.5080-5082) discloses an approach for halogenation of organic silaneswith chlorocarbons such as C₂Cl₆, and with other chlorocarbons ether arenot applicable for halogenation of silazanes or may not be used forindustrial process. Chlorination of organic silane ^(i)Pr₃SiH with C₂Cl₆was suggested to perform most efficiently in the neat silane inPongkittiphan et al.: ^(i)Pr₃SiH chlorination was completed in ˜1 h byC₂Cl₆ in presence of Pd/C.

Chlorination of TSA with C₂Cl₆ was attempted to demonstrate that thechlorination agent/catalyst suitable for organic silanes (Pongkittiphanet al.) is not applicable for the silazanes disclosed herein such asTSA.

TSA experiment disclosed herein was done as follows. Inside a glove box,C₂Cl₆ (2.67 g, 11.28 mmol) and Pd/C (0.43 g, 10% Pd load, 0.40 mmol Pd;predried under vacuum at 320° C. for 16 hours) were placed in a 20 mLvial. The vial was cooled to −36° C. and then precooled to −36° C. TSA(7.33 g, 68.29 mmol) was added. The vial was closed and the agitatedmixture was allowed to warm up to room temperature and stirred at roomtemperature for 5 hours 40 minutes, then filtered.

GC of filtrate: TSA 73.39%, TSA-Cl 1.13%, (SiH₃)₂N—SiH₂—O—SiH₃ 0.08%,{(H₃Si)₂N}₂(SiH₂) 0.30%, [(SiH₃)₂—N—SiH₂]₂—O 0.01%, [(SiH₃)₂NSiH₂]₂NH0.09%, C₂Cl₅H 1.18%, C₂Cl₆ 22.52%. Thus, TSA chlorination did notproceed with practically sufficient rate; the yield of TSA-Cl was lessthan 5%; reaction was not selective and produced TSA oligomers such as{(H₃Si)₂N}₂(SiH₂) and [(SiH₃)₂NSiH₂]₂NH.

This demonstrates that not any chlorocarbon/catalyst system may beutilized for selective chlorination of carbon-free silazanes.

More examples for interaction of TSA with C₂Cl₆ in the presence ofvarious catalyst are given in Table 3 below. The presented data supportthe statement above.

TABLE 3 Results of TSA chlorination with C₂Cl₆ Initial Catalyst TSA—ClTSA—Cl/ Selectivity TSA:C₂Cl₆ Solvent (mmol) T (° C.) Time yield (%)TSA—Cl₂ for TSA—Cl (r) 1.74 toluene no r.t. 66 h 2.0 No TSA—Cl₂ 93 1.87toluene Pd/C (0.58) 49.1 ± 0.5 4 h 30 min 1.2 1.43 40 1.68 toluene Pd/C(0.37) r.t. 17 h 0.6 0.40 16 6.06 TSA Pd/C (0.40) r.t. 5 h 40 min 4.02.63 49 1.74 toluene Pt/C (0.25) r.t. 17 h 0.0 1.00  6 1.60 tolueneB(Ph)₃ (0.35) r.t. 17 h 1.7 No TSA—Cl₂ 92

Comparative Example 8. Halogenation of TSA by Chlorocarbon Solvents

Prior art (e.g., Sommer et al. (“Stereochemistry of asymmetric silicon.XVIII. Hydrogen-halogen exchange of R3SiH with trityl halides”, L. H.Sommer, and D. L. Bauman, J. Am. Chem. Soc., 1969, vol. 91, p. 7076);Yanga et al. (“Reduction of Alkyl Halides by Triethylsilane Based on aCationic Iridium Bis(phosphinite) Pincer Catalyst: Scope, Selectivityand Mechanism”, J. Yanga and M. Brookhart, Adv. Synth. Catal., 2009,351, p. 175-187); and J Yang (“Iridium-Catalyzed Reduction of AlkylHalides by Triethylsilane”, by J. Yang; Brookhart, Maurice, from Journalof the American Chemical Society (2007), 129(42), 12656-12657) disclosedapproaches for halogenation of organic silanes with chlorocarbons suchas C₂Cl₆, and with other chlorocarbons either are not applicable forhalogenation of disclosed here silazanes or are not feasible for anindustrial process.

TSA experiment disclosed herein was done as follows. In each of three 2cc glass vials, TSA (0.2 ml) was blended with 1 ml of a chlorinatedsolvent: Methylene chloride (CH₂Cl₂), 1,1,1,2-Tetrachloroethane(C₂H₂Cl₄) and 1,2-Dichlorobenzene (C₆H₄Cl₂). The mixtures were analyzedby GC immediately and after 4 days.

The level of TSA-Cl in the first vial increased from 0.014 to 0.490%. Nopractically observable change in TSA-Cl concentration was detected inthe other two mixtures. This indicated that Methylene chloride mayexchange its Cl atom(s) for H with TSA but the rate of such reaction isnot practical.

Example 1: Synthesis of (SiH₃)₂N—SiH₂—NiPr₂ and of (SiH₃)₂N—SiH₂—NEt₂

300 g of diisopropylamine (3.0 mol) was charged to a 1-liter filterflask equipped with an overhead mechanical stirrer, a nitrogen bubbler,a chiller and a hydride scrubber as a reactor. 60 g (0.4 mol) ofchlorotrisilylamine was charged to a dropping funnel. The droppingfunnel was affixed to the reactor. A nitrogen sweep was added to thedropping funnel to prevent salt formation in the tip of the funnel. Thechiller was set to 18° C. and the chlorotrisilylamine was added viadropping funnel over a 1.5 hr period. The reactor temperature was set at22-23° C. during the addition. The reactor was allowed to stir for 0.5hr after the addition was complete.

The amine hydrochloride salt was then filtered. The filter cake wasrinsed with two 50 ml aliquots of diisopropylamine. The majority of thediisopropylamine was distilled off leaving 72 g of a crude product. Thecrude product was combined with other crude products from severalsmaller scale preparations of (SiH₃)₂N—SiH₂—NiPr₂ done in a similarfashion. (SiH₃)₂N—SiH₂—NiPr₂ was then distilled at 86° C. under a vacuumof −28 inches of mercury and 79 g of >99% pure product was collected.The overall yield was 56%. Table 4 shows vapor pressure data of(SiH₃)₂N—SiH₂—NiPr₂ estimated from the distillation and TSU data.

TABLE 4 Vapor pressure data of (SiH₃)₂N—SiH₂—NiPr₂ Temperature (° C.)Pressure (torr) 86 38 100 72 150 140

The synthesis of (SiH₃)₂N—SiH₂—NEt₂ proceeds similarly with the samemolar ratio, but replaces diisopropylamine with diethylamine.

Example 2: Synthesis of (SiH₃)₂N—SiH₂—NHiPr

300 g of isopropylamine (3.0 mol) was charged to a 1-liter filter flaskequipped with an overhead mechanical stirrer, a nitrogen bubbler, achiller and a hydride scrubber as a reactor. 60 g (0.4 mol) ofchlorotrisilylamine was charged to a dropping funnel. The droppingfunnel was affixed to the reactor. A nitrogen sweep was added to thedropping funnel to prevent salt formation in the tip of the funnel. Thechiller was set to 18° C. and the chlorotrisilylamine was added viadropping funnel over a 1.5 hr period. The reactor temperature was set at22-23° C. during the addition. The reactor was allowed to stir for 0.5hr after the addition was complete. The amine hydrochloride salt wasthen filtered. The filter cake was rinsed with two 50 mL aliquots ofisopropylamine. The majority of the isopropylamine was distilled offleaving 72 g of a crude product. The crude product was combined withother crude products from several smaller scale preparations of(SiH₃)₂N—SiH₂—NHiPr done in a similar fashion. (SiH₃)₂N—SiH₂—NHiPr wasthen distilled at 86° C. under a vacuum of −28 inches of mercury and 79g of >99% pure product was collected.

Example 3: Synthesis of (SiH₃)₂N—SiH₂—Br and of (SiH₃)₂N—SiH₂—N(SiH₃)₂

(SiH₃)₂N—SiH₂—Br and (SiH₃)₂N—SiH₂—N(SiH₃)₂ may be obtained by SnBr₄reacts with TSA:SnBr₄+H₃SiN(SiH₃)₂=BrH₂SiN(SiH₃)₂+(SiH₃)₂N—SiH₂—N(SiH₃)₂+SnBr₂+HBr. Aside product of the above reaction, HBr, may then be removed by areaction with the starting material TSA, i.e.,N(SiH₃)₃+4HBr=NH₄Br+3BrSiH₃. The synthesis process is as follows.

A round bottom flask with a PTFE-coated magnetic stir egg was chargedwith stoichiometric excess of TSA. If necessary, a solvent (e.g.,dodecane) and an HBr scavenger (e.g., tributylamine) may be added to theflask prior to adding TSA. The flask was fitted with a cold fingercondenser or a distillation head. A liquid addition funnel was attachedto the flask and charged with a solution of SnBr₄ in a solvent (such as,anisole or dodecane). The flask may then be cooled down and the SnBr₄solution was added dropwise to the flask. The headspace of the flask maybe kept under atmospheric pressure of nitrogen or at a reduced pressurein order to remove HBr as it forms.

After the addition was finished, the volatile products may be collectedby pulling vacuum through trap(s). The collected volatile products maythen be analyzed by GCMS. It was found that (SiH₃)₂N(SiH₂Br) and(SiH₃)₂N(SiH₂N(SiH₃)₂) were formed upon treating TSA with SnBr₄. Thefollowing byproducts were also identified: silane, bromosilane,dibromotrisilylamine. The solvents and unreacted SnBr₄ (in some cases)were also found.

The resulting (SiH₃)₂N—SiH₂—N(SiH₃)₂ was liquid at room temperature(˜22° C.), with a melting point of approximately −106° C. and a boilingpoint of approximately 131° C. The vapor pressure was calculated to be˜8 hPa at 27° C.

Example 4

The following PEALD testing was performed using a Picosun R200 PEALD 8″deposition tool with a 4″ wafer. The vapor of the mono-substituted TSAprecursor was delivered to the Picosun tool as shown in FIG. 1 .

ALD tests were performed using the (SiH₃)₂N—SiH₂—NiPr₂, which was placedin an ampoule heated to 70° C. and 02 plasma as oxidizing reactant.Typical ALD conditions were used with the reactor pressure fixed at ˜9hPa (1 hPa=100 Pa=1 mbar). Two 0.1-second pulses of the precursor vaporwere introduced into the deposition chamber via overpressure in theampoule using the 3-way pneumatic valve. The 0.1-second pulses wereseparated by a 0.5 second pause. A 4-second N2 purge removed any excessprecursor. A 16-second plasma 02 pulse was followed by a 3-second N2purge. The process was repeated until a minimum thickness of 300Angstrom was obtained. Depositions were performed with the substrateheated to 70° C., 150° C., and 300° C. Real self-limited ALD growthbehavior was validated as shown in FIG. 2 by increasing the number ofprecursor pulses within a given cycle.

ALD tests were also performed using the prior art SiH₂(NEt₂)₂ precursor,which was placed in an ampoule heated to 60° C. and O₂ plasma asoxidizing reactant. Applicants believe that SiH₂(NEt₂)₂ is currentlyused to deposit SiO₂ in several commercial processes. Typical ALDconditions were used with the reactor pressure fixed at ˜9 hPa (1hPa=100 Pa=1 mbar). Two 0.1-second pulses of the precursor vapor wereintroduced into the deposition chamber via overpressure in the ampouleusing the 3-way pneumatic valve. The 0.1-second pulses were separated bya 0.5 second pause. A 4-second N₂ purge removed any excess precursor. A16-second plasma O2 pulse was followed by a 3-second N₂ purge. Theprocess was repeated until a minimum thickness of 300 Ang was reached.Depositions were performed at 70° C., 150° C., 200° C., and 300° C. Asshown in FIG. 3 , the growth per cycle decreased with increasingtemperature. Table 5 summarizes the ALD results of SiH₂(NEt₂)₂ and(SiH₃)₂N—SiH₂—NiPr₂.

TABLE 5 Summarizes ALD results SiH₂(NEt₂)₂ (SiH₃)₂N—SiH₂—NiPr₂ Growthrate 70° C.¹ 1.42 Ang/cycle 3.10 Ang/cycle Growth rate 300° C.¹ 0.98Ang/cycle 2.05 Ang/cycle Wet Etch Rate 70° C.²  9.4 Ang/sec  8.8 Ang/secWet Etch Rate 150° C.²  7.2 Ang/sec  6.7 Ang/sec Wet Etch Rate 300° C.² 6.6 Ang/sec  6.7 Ang/sec Refractive index 70° C.³  1.432 1.460 Atomic %Carbon 70° C.⁴  0.05% TBD Atomic % Carbon 150° C.⁴  0.045% 0.015-0.03%Atomic % Hydrogen 150° C.⁴ ~10% ~10% Atomic % Nitrogen 150° C.⁴  0.015% 0.1% Within Wafer Non Uniformity⁵  2.84% 2.90% Notes: ¹Growth rate forfilms deposited at the stated temperatures ²Wet Etch Rate for filmsdeposited at the stated temperatures ³Refractive index for filmdeposited at 70° C. ⁴Atomic percentage in a film deposited at the statedtemperature as determined by Secondary lon Mass Spectrometry (SlMS).Hydrogen content is subject to uncertainty when measured by SlMS, as oneskilled in the art would recognize. ⁵Within Wafer Non Uniformity of afilm deposited at 200° C. as determined by ellipsometer over a 6 inchsilicon wafer. This parameter was not optimized and better uniformitywould be expected from an industrial tool.

As can be seen, the growth rate for films produced by(SiH₃)₂N—SiH₂—NiPr₂ is much better than those of SiH₂(NEt₂)₂ at both 70°C. and 300° C. At 70° C., (SiH₃)₂N—SiH₂—NiPr₂ has a much better wet etchrate and refractive index than SiH₂(NEt₂)₂, which both indicateformation of a much better, denser oxide film.

Example 5

ALD tests to deposit N-doped silicon oxide were performed using the(SiH₃)₂N—SiH₂—NiPr₂, which was placed in an ampoule heated to 70° C., O₂plasma as oxidizing reactant and NH₃ plasma as an additional reactant.Typical ALD conditions were used with the reactor pressure fixed at ˜9hPa. Two 0.1-second pulses of the precursor vapor were introduced intothe deposition chamber via overpressure in the ampoule using the 3-waypneumatic valve. The 0.1-second pulses were separated by a 0.5 secondpause. A 4-second N₂ purge removed any excess precursor. A 16-secondplasma O₂ pulse was followed by a 3-second N₂ purge. Two 0.1-secondpulses of the precursor vapor were introduced into the depositionchamber via overpressure in the ampoule using the 3-way pneumatic valve.The 0.1-second pulses were separated by a 0.5 second pause. A 4-secondN₂ purge removed any excess precursor. An 11-second plasma NH₃ pulse wasfollowed by a 3-second purge. The entire process (precursor-plasmaO₂-precursor-plasma NH₃) was repeated until the thickness reached atleast 300 Ang. Depositions were performed at 150° C.

The resulting SiO₂ film had a wet etch rate of 3.2 Ang/sec and Nconcentration of ˜1%. Such a low etch rate is found to be beneficial forspacer-based double patterning to enable a low edge roughness in thetransfer layer when the ALD-deposited silicon oxide film is used as amask. The person ordinary skilled in the art would recognize that theOxygen to Nitrogen content in the obtained film can be tuned byadjusting the number, sequence or/and duration of the O containingreactant and N containing reactant pulses. Applicant believes that a Nconcentration of approximately 0.5% to approximately 5% in an SiO₂ filmis beneficial for the spacer-defined patterning applications.

Example 6

ALD tests were performed using the (SiH₃)₂N—SiH₂—N(SiH₃)₂, which wasplaced in an ampoule heated to 26° C. and O₂ plasma as oxidizingreactant. Typical ALD conditions were used with the reactor pressurefixed at ˜9 hPa. Three 0.1-second pulses of the precursor vapor wereintroduced into the deposition chamber via overpressure in the ampouleusing the 3-way pneumatic valve. The 0.1-second pulses were separated bya 0.5 second pause. A 4-second N₂ purge removed any excess precursor. A16-second plasma O₂ pulse was followed by a 3-second N₂ purge. Theentire process (precursor-plasma O2-) was repeated until the thicknessreached at least 300 Ang. As shown in FIG. 4 , the growth per cycleincreased with increasing deposition temperatures from 150° C. to 300°C. FIG. 4 also shows comparative growth per cycle results of five0.1-second pulses versus three 0.1-second pulses. Both wereapproximately 0.6 A/cycle, indicating true ALD saturation because thelarger amounts of precursor introduced via 5 pulses do not result in ahigher growth rate than the film produced by 3 pulses.

The growth rate was approximately 0.58 Ang/cycle at 150° C. and resultedin a film having a refractive index of 1.45. For comparison, attempts togrow an SiO₂ film by ALD using pure TSA in similar conditions have notyielded any films, thus proving the benefit of the chemicalfunctionalization to enhance the reactivity with the surface hydroxylgroups.

Example 7. Halogenation of TSA with Ph₃CCl with Catalysts

Reactions with catalysts were performed at the similar conditions andloads to show the effect of catalysts on the reaction rate. Reactionswithout any catalyst are also presented at the same conditions forcomparison. Amounts of starting compounds, temperatures, reaction timesare shown Table 6. All reactions were performed in a glove box undernitrogen with less than 0.5 ppm of oxygen.

TABLE 6 Results of TSA chlorination with the catalysts Amounts ofTSA—Cl/ TSA:Ph₃CCl Reaction TSA—Cl TSA—Cl₂ in Selectivity Reaction N(mmol) Catalyst (mmol) T (° C.) Time yield (%) products (r, %) 112.6:7.5  No r.t. 17 h  1 44  69*  1a 52.4:29.6 No 48.6 ± 0.5 4 h 20 min 2 61  78* 2 12.2:6.9  Pt(10%)/C, 0.30 r.t. 17 h 17 15 85  2a 25.3:14.4Pt(10%)/C, 0.63 48.4 ± 0.8 4 h 20 min 31  7 83 3 11.7:7.0  Pd(10%)/C,0.40 r.t. 17 h 43  7 78  3a 21.1:12.9 Pd(10%)/C, 0.61 49.3 ± 2.4 4 h 20min 41  7 74 4 12.6:6.9  BPh₃, 0.33 r.t. 17 h 19 76 97  4a 23.4:14.0BPh₃, 0.70 49.1 ± 1.2 4 h 15 min 19 67 97 5 13.14:7.68  Ru(5%)/C (0.23)r.t. 17 h 16 28 86 6 27.5:14.7 Ru(5%)/C (0.47) 64.6 ± 1.0 2 h 10 min 37 8 80 7 26.8:13.9 Ru(5%)/C (0.45) 80.0 ± 1.0 1 h 25 min 48  8 78 Noteherein: Yield of TSA—Cl calculated from Ph₃CCl by reaction: Ph₃CCl +(H₃Si)₃N = (H₃Si)₂N(SiH₂Cl) + Ph₃CH from GC data and applying equation:Yield (%) = 100 · η_(TSA (mmol))/{(I_(TSA)/I_(TSA—Cl) ·M_(TSA—Cl)/M_(TSA) + 1) · η_(Ph3CCl (mmol))}, where η_(TSA (mmol)) andη_(Ph3CCl (mmol)) are amounts in mmol of TSA and Ph₃CCl taken forreaction, I_(TSA)/I_(TSA—Cl) ratio of relative intensities of TSA andTSA—Cl in GC of reaction mixture, M_(TSA—Cl)/M_(TSA) ratio of molarweights of TSA and TSA—Cl. *high error in selectivity is possible due tolow intensity of signals.

Activity of catalysts is as follows: Pd/C>Pt/C≈Ru/C>BPh₃>>reaction nocatalyst in toluene. Selectivity of catalysts is BPh₃>Pt/C≈Ru/C>Pd/C.Application of Pd(10%) on carbon allows to prepare TSA-Cl with nearly40% yield in 4 hours 20 min. Reaction accelerates with the catalyst bymoderate heating without loss of selectivity. Table 7 shows GC data forTSA chlorination in Example 7.

TABLE 7 GC data for TSA chlorination in Example 7 Reaction TSA TSA-ClTSA-Cl₂* Other lmpurities N (% in GC) (% in GC) (% in GC) (%) 1 14.7350.131 0.003 0.06 1a 13.374 0.183 0.003 0.05 2 11.454 1.597 0.11 0.17 2a9.551 2.716 0.37 0.19 3 7.253 3.359 0.50 0.46 3a 4.687 2.048 0.29 0.41 414.145 2.136 0.03 0.06 4a 9.41 1.599 0.02 0.04 5 8.75 1.19 0.04 0.15 611.01 3.58 0.45 0.44 7 8.94 3.92 0.47 0.65 Note herein:*For TSA-Cl₂,Given in Table 7 is a total of two isomers (H₃Si)₂N(SiHCl₂) and(H₃Si)N(SHCl)₂, relative amount of one (H₃Si)N(SiHCl)₂ is significantlyhigher than that of (H₃Si)₂N(Si elative amount of one (H₃Si)N(SiHCl)₂ issignificantly higher than that of (H₃Si)HCl₂) in all examples shownherein. Other impurities are SiH₄, SiH₃Cl, SiH₂Cl₂, {(H₃Si)₂N}₂(SiH₂)and oligomeric aminosilanes.

a) Procedure for room temperature reaction 1 (comparative reactionwithout catalyst): Ph₃CCl was placed in a 20 mL vial and dissolved inToluene (7.1 g). Then TSA was added, the vial was closed and thereaction mixture was stirred for 17 hours at room temperature. Afterthat, an aliquot was taken for GC analysis.

b) Procedure for reaction 1a: Ph₃CCl placed in a 100 mL three neckedflask equipped with a thermocouple and a reflux condenser with coolingset to −30° C. Toluene (34 g) was added and Ph₃CCl was dissolved. TSAwas added and the reaction mixture was stirred at 1 atm N₂ for 4 hours20 min by heating at 48.6±0.5° C. with the oil bath. Then the flask wasremoved from oil bath, closed with a glass stopper and quickly cooled toroom temperature. An aliquot was taken for GC analysis.

c) Procedure for room temperature reactions 2, 3 and 5 (Pt/C, Pd/C andRu/C catalysts): Ph₃CCl and the required amount of the catalyst wereplaced in a 20 mL vial. Toluene (72-7.6 g) was added to dissolve Ph₃CCl.TSA was added, the vial was closed and the reaction mixture was stirredfor 17 hours at room temperature. After that, the mixture was quicklyfiltered through a 0.2 μ-M PTFE filter and an aliquot of the filtratewas taken for GC analysis. GC of products with Pd/C catalyst is shown inFIG. 7 . Keeping reaction mixture several days with Pt/C or Pd/Ccatalysts resulted in loss of selectivity, e.g. GC of the mixture withPd/C catalyst after 9 days contained: SiH₄, 0.17%, MCS, 0.38%, DCS0.03%, TSA, 0.77%, TSA-Cl, 1.62%, TSA-Cl₂, 0.04 & 0.55%, AMS-3, 2.9%,Toluene, 76.1%, mixture of TSA oligomers (chlorinated & non chlorinated)2.4%, Ph₃CR (R=H, Cl) 15.9%. AMS-3={(H₃Si)₂N}₂(SiH₂), MCS=SiH₃Cl,DCS=SiH₂Cl₂, TSA-Cl2=two isomers (H₃Si)₂N(SiHCl₂) and (H₃Si)N(SiH₂Cl)₂.FIG. 7 is a GC chromatogram of solution Ph₃CCl-TSA and Pd/C₁₋₄ h 20 minheating illustrating selectivity of chlorination toward the TSA-Cl.

d) Procedure for reactions 2a, 3a (Pt/C, Pd/C catalysts): Ph₃CCl wasplaced in a 100 mL three necked flask equipped with a thermocouple and areflux condenser with cooling set to −30° C. The required amount of thecatalyst was introduced and toluene (17-25 g) was added to dissolvePh₃CCl. TSA was added, the flask was closed with the stopper and thereaction mixture was stirred at 1 atm N₂ for 4 hours 20 min while heatedby an oil bath. Then the flask was removed from the oil bath, closedwith the glass stopper and quickly cooled to room temperature. Thecontent was quickly filtered through the 0.2 μ-M PTFE filter and analiquot of the filtrate was taken for GC analysis. GC of products withPt/C catalyst is shown in FIG. 8 , which is a GC chromatogram ofsolution Ph₃CCl-TSA and Pt/C₁₋₄ h 20 min heating illustratingselectivity of chlorination toward the TSA-Cl.

e) Procedure for room temperature reaction 4 (BPh₃ catalyst): Ph₃CCl(1.92 g, 6.89 mmol) was placed in a 20 mL vial and dissolved in toluene(4.4 g). Then TSA (1.35 g, 12.58 mmol) was added, the mixture wasstirred for 15 min and then a solution of BPh₃ (0.08 g, 0.33 mmol) in2.8 g of toluene was added to the mixture. The vial was closed and thereaction mixture was stirred for 17 hours at room temperature. Analiquot is taken for GC analysis.

f) Procedure for reaction 4a: Ph₃CCl (3.90 g, 13.99 mmol) was placed ina 100 mL three necked flask equipped with a thermocouple and a refluxcondenser with cooling set to −30° C. Toluene (15.7 g) was added todissolve Ph₃CCl. TSA (2.51 g, 23.39 mmol) was added, the mixture wasstirred for 15 min at room temperature and then a solution of BPh₃ (0.17g, 0.70 mmol) in 4.7 g of toluene was added to the mixture. The flaskwas closed with the stopper and the reaction mixture was stirred at 1atm N₂ for 4 hours 15 min while heated at 49.1±1.2° C. by an oil bath.Then the flask was removed from oil bath, closed with glass stopper andquickly cooled to room temperature. An aliquot was taken for GCanalysis. The results of reactions 4 and 4a are provided in Table 7. Themajor reaction product is TSA-Cl, the minor product is TSA-Cl2(H₃Si)N(SiH₂Cl)₂. FIG. 9 is a GC chromatogram of solution Ph₃CCl-TSA andBPh₃, 4 h 15 min heating illustrating selectivity of chlorination towardthe TSa-Cl.

g) Procedure for reactions 6, 7 (Ru/C catalyst): In the glove box,Ph₃CCl (all amounts see Table 7) was placed in a 100 mL pressure ratedglass tube equipped with a thermocouple and a pressure gauge. Therequired amount of the catalyst was introduced and toluene (13.4, 13.6g) added. Then TSA added (all amounts see Table 7), the tube was closedand the reaction mixture was stirred/heated in an oil bath at 65° C. for2 h 10 min (reaction 6) and 80° C. for 1 h 25 min (reaction 7). Thepressure was monitored by the gauge. Then the tube was taken out fromthe oil bath, quickly cooled down to room temperature and placed in thefreezer at −36° C. for 1 h 30 min. The cold solution was filteredthrough the 0.45 μ-M PTFE filter and an aliquot of the filtrate wastaken for GC analysis. GC of products with Ru/C catalyst, reactions 6and 7 is presented in Table 7.

Part of solution (14.87 g) obtained after filtration of the reactionmixture 6 was placed in a 100 mL two necked flask and the volatiles werecollected in the cold trap (−80° C.) under the static vacuum. Remainedin the pot: 2.93 g of a non-volatile material. Collected in the trap:11.94 g of volatiles. The GC analysis: SiH₃Cl (0.02%), SiH₂Cl₂ (0.01%),TSA (12.12%), (SiH₃)₂N—SiH₂—O—SiH₃ (0.02%), TSA-Cl (3.95%),(H₃Si)₂N(SiHCl₂) (0.09%), (H₃Si)N(SiHCl)₂ (0.35%), {(H₃Si)₂N}₂(SiH₂)0.01%, toluene (83.25%), heavier aminosilanes in total (0.12%). Yield ofTSA-Cl in volatile fraction is 32%. For reaction 6, reacted TSA notforming TSA-Cl, TSA-Cl₂: 11%, implying a high selectivity of reaction.

The examples disclosed in Example 7 clearly illustrate that thepresented catalysts selectively accelerate chlorination of TSA. Thesummary of the catalysts used in the disclosed examples herein is asfollows.

1) BPh₃ has never been suggested/reported as a catalyst for chlorinationof silazanes and silanes. Application of BPh₃ may not be an obvious stepbecause a related compound B(C₆F₅)₃ is known to polymerize TSA withpreviously suggested chlorination catalyst. Yet, as it is proved inthese examples listed herein, BPh₃ does not polymerizes TSA, butpromotes a selective chlorination.

2) Pd/C has been suggested for chlorination only for substituted silane^(i)Pr₃SiH with hexachloroethane, but not for TSA with Ph₃CCl.Selectivity of Pd/C is lowest among presented catalysts.

3) Pt/C and Ru/C have never been suggested before for chlorination ofsilazanes. Both heterogeneous catalysts are active and selectivelychlorinate TSA producing TSA-Cl and TSA-Cl₂. These are thus preferredfor a large-scale process based on a flow through or pot reaction.

4) Selectivity of the reaction may depend on relative amounts of thereagents and on the degree of conversion, e.g. if the reaction is pushedto full consumption of Ph₃CCl, the resulted long exposure of TSA/TSA-Clto the catalyst leads to loss of selectivity.

Example 8. Halogenation of TSA with Ph₃CCl in Various Solvents

Inside a glove box, five 20 ml glass vials were charged with 1 g (3.6mmol) of Ph₃CCl, each. 3.6 ml of a solvent was added to each vial todissolve the solids. Here the solvent is selected from PhCl, PhCl₂,C₂Cl₄H₂, PhCF₃* or CH₂Cl₂. Then 0.69-0.75 g (6.4-7.0 mmol) of TSA wereadded to each vial. The progress of the reaction was monitored by GC.Note: *as Trityl Chloride solubility in PhCF₃ was not sufficient, inthis case, 7.2 ml of PhCF₃ was used.

The rate and selectivity of the halogenation are illustrated in FIG. 10and Table 8. FIG. 10 is Kinetic of TSA-Cl accumulation in the reactionmixture in various solvents, i.e., TSA-Cl concentration vs time invarious solvents.

TABLE 8 Selectivity of TSA chlorination in various solvents ConversionSelectivity Selectivity (by TSA-Cl/TSA (by TSA-Cl₂/TSA CoefficientSolvent peak ratio) peak ratio) γ, % PhCl 0.26 7.9 74 PhCl₂ 0.52 23 78C₂Cl₂H₂ 0.14 22.3 49 PhCF₃ 0.06 0.7 30 CH₂Cl₂ 1.04 64.8 86

The results in Table 8 show that the rate of TSA chlorination andreaction selectivity depend strongly on the solvent. The rate ofreaction goes down in the sequence: CH₂Cl₂>PhCl₂>C₂Cl₄H₂˜PhCl>PhCF₃.CH₂Cl₂ (methylene chloride) and PhCl₂ (o-dichlorobenzene) media offerthe best selectivity of the process.

Example 9 Halogenation of TSA with Ph₃CCl in Toluene at High Temperatureand High Pressure

Inside a glove box, a 150 mL pressure rated glass flask equipped with amagnetic stirring bar, a thermocouple and a pressure gauge was chargedwith 12.42 g (44.6 mmol) of Trityl chloride, 41.15 g of Toluene(anhydrous toluene from Aldrich) and 11.43 g (106.5 mmol) of TSA. Theflask sealed and heated under stirring in an oil bath to 90° C., thenkept 7 hours at 90° C. Pressure initially reached 15 psig at 90° C.,then dropped to 14 psig during 3 hours and was stable at 14 psig to theend of experiment. After 7 hrs, the reaction mixture was cooled to roomtemperature, while pressure dropped to 0 psig, then placed in thefreezer, Ph₃CH crystallized, aliquote of liquid analyzed by GC: SiH₃Cl(0.11%), TSA (14.13%), TSA-Cl (10.02%), TSA-Cl₂ (0.03%), TSA-Cl₂(0.47%), Toluene (74.07%). Ph₃CH (1.00%). TSA-Cl yield: 76%.

TSA chlorination by Ph₃CCl in toluene at 52° C. and below and at normalpressure is slow (yield of TSA-Cl is 2% at 48.6±0.5° C. for 4 h 20 min)and is not suitable for industrial synthesis. However, the selectivechlorination may be accomplished within several hours at 87-90° C./aboveatmospheric pressure (higher than boiling point of TSA 53° C.) withsubstantial TSA-Cl yield. This solution is not obvious since 1)syntheses are not normally considered above boiling point of reagents ifreactions are not proceeding up to boiling point, 2) aminosilanes tendto decompose at higher temperatures and hence temperatures higher thanboiling point in aminosilane chemistry are normally avoided.

Example 10. Halogenation of TSA with Ph₃CCl in Xylene at HighTemperature and High Pressure, Followed by Separation of Ph₃CH andDistillation of Reaction Products

Inside a glove box, a 150 mL pressure rated glass flask equipped with amagnetic stirring bar, a thermocouple and a pressure gauge was chargedwith 30.02 g (0.11 mol) of Ph₃CCl, 40.3 g of xylenes (pre dried overmolecular sieves) and 13.06 g (0.12 mol) of TSA. The flask sealed andheated under stirring in an oil bath to 90° C., then kept 5.5 hours at90° C. Pressure initially reached 14.2 psig at 90° C., then dropped to10 psig during 3 hours and was stable at 10 psig to the end ofexperiment. After 6 hrs, the reaction mixture was cooled to roomtemperature, while pressure dropped to 0 psig, and placed in the freezerat −35° C. for 18 hours. Solid deposited at low temperature (46.14 g)separated by filtration and the obtained liquid stripped under vacuum inthe trap cooled with liquid nitrogen. Collected in the trap 30.53 g ofliquid, remaining undistilled 6.73 g.

GC of deposited solid (0.09 g of solid in 0.42 g of toluene): TSA(0.08%), TSA-Cl (0.53%), TSA-Cl2 (0.07%), toluene (90.93%), xylenes(2.61%), Ph₃CH (5.76%). GC of stripped liquid: SiH₃Cl (0.21%), SiH₂Cl₂(0.13%), TSA (8.86%), TSA-Cl (22.82%), TSA-Cl₂ (0.20%), TSA-Cl₂ (2.95%).(H₃Si)₂N(SiH₂)N(SiH₃)₂ (0.05%), Xylenes (64.68%). TSA-Cl isolated yield:45%. GC of liquid remaining undistilled during stripping: TSA-Cl₂(0.22%), Xylenes (73.96%), Ph₃CH (25.69%).

This example illustrates that the reaction could be scaled up. Almostall formed triphenyl methane could be crystallized and separated byfiltration, while all TSA and TSA-Cl stripped from the reaction mixture(from filtrate obtained after separation of triphenylmethane). TSA-Clisolated yield: 45% at the presented ratio of starting compound andpresented process pathway.

Example 11. Halogenation of TSA with Ph₃CCl in Xylene at HighTemperature and High Pressure Followed by Distillation of ReactionProducts Directly from the Reaction Mixture

Inside a glove box, a 440 mL pressure rated glass flask equipped with amagnetic stirring bar, a thermocouple and a pressure gauge was chargedwith 91.38 g (0.33 mol) of Trityl chloride, 120.48 g of Xylenes (predried over molecular sieves) and 50.05 g (0.47 mol) of TSA. The flasksealed and heated under stirring in an oil bath to 90° C., then kept 5hours at 90° C. Pressure initially reached 18 psig at 90° C., thendropped to 13 psig during 3 hours and was stable at 13 psig to the endof experiment. After 5 hrs, the reaction mixture was stripped during 30min in the trap cooled with liquid nitrogen under a static vacuum.Temperature during the stripping initially dropped to 80.8° C. and thengradually increased to 85.5° C., while pressure gradually decreased to160 Torn during the stripping. After 30 min stripping stopped, reactionmixture cooled to room temperature, collected distillate in the trap waswarmed to room temperature, weighted and analyzed by GC.

Weight of reaction mixture after stripping is 207.9 g. GC of reactionmixture after stripping: TSA (0.17%), TSA-Cl (6.51%), TSA-Cl2 (0.09%),TSA-Cl2 (1.63%), (H₃Si)₂N(SiH₂)N(SiH₃)₂ (0.05%), Xylenes (65.41%), Ph₃CH(26.00%). More TSA-Cl and TSA-Cl₂ was obtained from this mixture bystripping at vacuum below 160 torr.

Weight of stripped liquid is 51.3 g. GC of reaction mixture afterstripping: SiH₃Cl (0.65%), SiH₂Cl₂ (0.26%), TSA (39.61%), TSA-Cl(42.50%), TSA-Cl2 (0.13%), iso-TSA-Cl₂ (1.36%), (H₃Si)₂N(SiH₂)N(SiH₃)₂(0.05%), Xylenes (15.38%). TSA-Cl isolated yield in stripped liquid:47%. Total yield of TSA-Cl 75.5%. Reacted Ph₃CCl not forming TSA-Cl &TSA-Cl₂: 31.5 mmol. Selectivity: 90.5%.

This example illustrates scalability of the process. All TSA, TSA-Cl maybe directly stripped from the hot reaction mixture illustratingefficiency of the presented approach.

Example 12. Bromination of BDSASi with Ph₃CBr in Methylene Chloride

Inside a glove box, a 2 cc glass vial was charged with 0.9 mmol ofPh₃CBr. To the vial, 0.9 ml of Methylene Chloride was added followed by1.45 equivalents of BDSASi.

GC analysis shown BDSASi bromination was complete after 22 hours. Theestimated yield of BDSASi-Br was 12%. GC of reaction mixture (1.45BDSASi:Ph₃CBr): SiH₃Br (0.15%), TSA (0.33%), CH₂Cl₂ (81.64%),(H₃Si)₂N(SiH₂Br) (0.77%), (H₃Si)₂N(SiH₂)N(SiH₃)₂ (8.03),((H₃Si)₂N(SiH₂))₂NH (0.06%), BDSASi-Br (0.35%), iso-BDSASi-Br (1.28%),((H₃Si)₂N)₃SiH (0.55%), oligomeric aminosilanes [Si₈N₄H₂₂] (0.09%),[Si₉H₂₄N₄] (0.19%), Ph₃CH (6.05%).

i. Compound (H₃Si)₂N(SiH₂Br). Observed in mass spectrum multiplet withmaximum at m/z=184, is formed mostly by [M-H]⁺ (Si₃H₇NBr) overlappedwith weak [M]⁺ and [M-H₂]⁺. Observed patterns for [M-H]⁺ (Si₃H₇NBr) aresimilar to calculated ones for [Si₃H₇NBr]⁺ (m/z=184). MS(H₃Si)₂N(SiH₂Br): multiplet m/z=182-190 with maximum at m/z=184 [M-H]⁺overlapped with weak [M]⁺, [M-H₂]⁺, [M-3H]⁺ (100%), multipletm/z=150-156 [M-SiH₃]⁺, [M-SiH₄]⁺, [M-HSiH₄]⁺ (40%). Mass spectra of twoisomers BDSASI-Br are similar. FIG. 11 is the mass spectra of theBDSASi-Br (bis-Disilylaminosilyl bromide,(SiH₃)₂N—SiH₂—N(SiH₃)(SiH₂Br)).

ii. Compound BDSASi-Br. Observed in mass spectrum multiplet with maximumat m/z=261 is from [M-H]⁺ (Si₅H₁₂N₂Br). Observed patterns for [M-H]⁺(Si₅H₁₂N₂Br) are similar to calculated ones for [Si₅H₁₂N₂Br]⁺ (m/z=261).MS BDSASI-Br: 261 [M-H]⁺ (15%), 229 overlapped with 227 [M-SiH₃]⁺,[M-SiH₄—H]⁺ (100%), 197 [M-SiH₄—SiH₃]⁺ (10%), overlapped multiplet145-151 [M-SiH₄—Br]⁺, [M-SiH₃—Br]⁺, [M-SiH₃—HBr]⁺, [M-SiH₄—HBr]⁺ (70%).FIG. 12 GC Chromatogram of 1M Ph₃CBr/CH₂Cl₂+1.45 eq. BDSASi reactionmixture.

Example 13 Chlorination of BDSASi with Ph₃CCl in Methylene Chloride

Reaction mixture with Ph₃CCl was prepared as in example 12.1. BDSASichlorination was not detected after 24 hrs and 0.01 g of BPh₃ catalystwas added to the solution. GC showed completion of the reaction within 2hours. The estimated yield of BDSASi-Cl was 47%. The ratio of BDSASi-Clto BDSASi-Cl2 peaks is 6.0.

(H₃Si)₂N(SiH₂)N(SiH₃)₂ (BDSASi) chlorination with initial ratioBDSASi:Ph₃CCl=3:1 proceeded with the BDSASi-Cl yield 66% and the ratioof BDSASi-Cl to BDSASi-Cl2 12.6. GC of reaction mixture(3BDSASi:1Ph₃CCl): CH₂Cl₂ (66.04%), (H₃Si)₂N(SiH₂)N(SiH₃)₂ (18.07),BDSASi-Cl (2.46%), iso-BDSASI-Cl (4.58%), BDSASi-Cl₂ (0.27%),iso-BDSASI-Cl₂ (0.28%), oligomeric aminosilanes Si₈H₂₄N₄ (0.50%),Si₉H₂₃N₄Cl (0.32%), Ph₃CH (6.68%), BPh₃ (0.04%). Mass spectra of twoisomers BDSASI-Cl are similar. FIG. 13 is one of the mass spectra ofBDSASi-Cl (bis-Disilylaminosilyl chloride,(SiH₃)₂N—SiH₂—N(SiH₃)(SiH₂Cl)).

i. Compound BDSASI-Cl. Observed in mass spectrum multiplet with maximumat m/z=215 is mostly by [M-H]⁺ (Si₅H₁₂N₂Cl) with a small impact of [M]⁺.Observed patterns for [M-H]⁺ (Si₅H₁₂N₂Cl) are similar to calculated onesfor [Si₅H₁₂N₂Cl]⁺ (m/z=215). MS BDSASi-Cl: 216 [M]⁺ overlapped with 215[M-H]⁺ (20%), 185 [M-SiH₃]⁺ overlapped with 183 [M-SiH₄]⁺, 181 [M-Cl]⁺,179 [M-HCl]⁺ (100%), 145-153 multiplet (50%). Mass spectra of twoisomers of BDSASi-Cl₂ are similar. FIG. 14 is one of the mass spectra ofBDSASi-Cl₂ (bis-disilylaminosilyl dichloride,(SiH₃)₂N—SiH₂—N(SiH₂Cl)₂)).

ii. Compound BDSASI-Ch. Observed in mass spectrum multiplet with maximumat m/z=249 is formed by [M-H]⁺ (Si₅H₁₁N₂Cl₂). Observed patterns for[M-H]⁺ (Si₅H₁₁N₂Cl₂) are similar to calculated ones for [Si₅H₁₁N₂Cl₂]⁺(m/z=249). MS BDSASi-Cl₂:249 [M-H]⁺ (20%), multiplet with m/z=213-221due to [M-SiH₃]⁺, [M-SiH₄]⁺, [M-Cl]⁺, [M-HCl]⁺ (100%), multiplet withm/z=179-185 due to [M-2SiH₃]⁺, [M-SiH₃—Cl]⁺, [M-SiH₃—HCl]⁺, etc. (80%).FIG. 15 GC Chromatogram of 1M Ph₃CCl/CH₂Cl₂+1.45 eq. BDSASi reactionmixture.

Example 14. Halogenation of TSA-Cl with Ph₃CBr in Methylene Chloride

Inside a glove box, a 2 cc glass vial was charged with 0.9 mmol ofPh₃CBr, 0.9 ml of Methylene Chloride and 1.45 equivalents of TSA-Cl. GCanalysis showed that TSA-Cl bromination was complete after 48 hourssince signal of Ph₃CCl was absent on the chromatogram. The estimatedyield of TSA-Br was 17%.

Based on the GC data reaction may proceed by the following equation:3(H₃Si)₂N(SiH₂Cl)+3Ph₃CBr=(H₃Si)₂N(SiH₂Br)+(H₃Si)N(SiH₂Cl)₂+(H₃Si)N(SiH₂Br)₂+3Ph₃CH.

CG of reaction mixture after 48 h (1.45 BDSASi:Ph₃CBr): SiH₃Cl (0.05%),SiH₂Cl₂ (0.12%), CH₂Cl₂ (80.45%), (H₃Si)₂N(SiH₂Cl) (8.08%),(H₃Si)₂N(SiH₂Br) (1.70%), (H₃Si)₂N(SiH₂Cl₂) (0.17%), (H₃Si)N(SiH₂Cl)₂(2.03%), (H₃Si)N(SiH₂Br)₂ (1.15%), Ph₃CH (5.90%). MS of (H₃Si)₂N(SiH₂Br)refers to Example 10.

Compound (H₃Si)N(SiH₂Br)₂. Observed in mass spectrum multiplet withmaximum at m/z=264 is formed by [M-H]⁺ (Si₃H₆NBr₂). Observed patternsfor [M-H]⁺ (Si₃H₆NBr₂) are similar to calculated ones for [Si₃H₆NBr₂]⁺(m/z=264). MS (H₃Si)N(SiH₂Br)₂: 264 [M-H]⁺ (100%), 232 [M-H—SiH₄]⁺(15%), 184 [M-HBr]⁺ (70%), 152 [M-HBr—SiH₄]⁺ (70%). FIG. 16 GCChromatogram of 1M Ph₃CBr/CH₂Cl₂+1.45 eq. TSA-Cl reaction mixture.

Five compounds, (H₃Si)₂N(SiH₂Br), BDSASi-Br, BDSASi-Cl, BDSASi-Cl₂ and(H₃Si)N(SiH₂Br)₂, are synthesized in Examples 12 to 14 as a result ofapplication of the disclosed method for selective chlorination ofaminosilanes with i) Ph₃CCl or ii) Ph₃CCl without and with a catalyst.

Examples 15. Chlorination of (H₃Si)₂N(SiH₂(N^(i)Pr₂

Preparation followed the procedure shown in Example 7.2. New compounds,(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)), (H₂SiCl)₂N(SiH₂(N^(i)Pr₂)),(H₃SiCl)N(SiH₂(N^(i)Pr₂))₂, are synthesized herein as a result ofapplication of the disclosed method for selective chlorination ofaminosilanes with Ph₃CCl and applying a catalyst.

Reactions started with mixing (H₃Si)₂N(SiH₂(N^(i)Pr₂)) (2.0 g, 9.7mmol), Ph₃CCl (2.12 g, 7.6 mmol), Pd/C (0.54 g, 10% Pd, 0.5 mmol),toluene (7 g). CG of filtered reaction mixture: (H₃Si)₂N(SiH₂Cl)(1.23%), toluene (78.70%), (H₃Si)₂N(SiH₂(N^(i)Pr₂)) (6.44%),(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)) (3.02%), (H₂SiCl)₂N(SiH₂(N^(i)Pr₂))(0.16%), (H₃Si)N(SiH₂(N^(i)Pr₂))₂ (1.28%), (H₃SiCl)N(SiH₂(N^(i)Pr₂))₂(0.36%), Ph₃CH (7.93%). The yield of (H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)) is77% from Ph₃CCl assuming that chlorination proceeds by equation:3(H₃Si)₂N(SiH₂(N^(i)Pr₂))+2Ph₃CCl=(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂))+(H₃Si)₂N(SiH₂Cl)+(H₃Si)N(SiH₂(N^(i)Pr₂))₂+Ph₃CH.

i. Compound (H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)). Observed in mass spectrumpatterns of molecular ion assigned to (H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂))are similar to calculated ones for [C₆H₂₁N₂Si₃Cl]⁺ (m/z=240). MS(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)): 240 [M]⁺ overlapped with 239 [M-H]⁺(10%), 225 [M-Me]⁺ (100%), 195 [M-Me-SiH₃]⁺ (15), 181 [M-H^(i)Pr—CH₄]⁺overlapped with 183 [M-^(i)Pr-Me]⁺ (80%), 155 [M-C₆H₁₃]⁺ overlapped with153 [M-H^(i)Pr—^(i)Pr]⁺ overlapped with 151 [M-SiH₃—^(i)Pr-Me]⁺ (15),140 [M-N^(i)Pr]⁺ (30%).

ii. Compound (H₂SiCl)₂N(SiH₂(N^(i)Pr₂)). Observed in mass spectrumpatterns of molecular ion assigned to (H₂SiCl)₂N(SiH₂(N^(i)Pr₂)) aresimilar to calculated ones for [C₆H₂₀N₂Si₃Cl₂]⁺ (m/z=274). MS(H₂SiCl)₂N(SiH₂(N^(i)Pr₂)): 274 [M]⁺ (5%), 259 [M-Me]⁺ (100%), 229[M-H₂-^(i)Pr]⁺ overlapped with 231 [M-^(i)Pr]⁺ (10%), 215 [M-CH₄—Pr]⁺overlapped with [M-N^(i)Pr]⁺ (80%), 174 [M-N^(i)Pr₂] (40%).

iii. Compound (H₃SiCl)N(SiH₂(N^(i)Pr₂))₂. Observed in mass spectrumpatterns of molecular ion assigned to (H₃SiCl)N(SiH₂(N^(i)Pr₂))₂ aresimilar to calculated ones for [C₁₂H₃₄N₃Si₃Cl]⁺ (m/z=339). MS(H₃SiCl)N(SiH₂(N^(i)Pr₂))₂: 339 [M]⁺ (1%), 324 [M-Me]⁺ (1%), 296[M-^(i)Pr]⁺ (1%), 239 [M-N^(i)Pr₂]⁺ (70%), 223 [M-CH₄—N^(i)Pr₂]⁺overlapped with 225 [M-NC₇H₁₆]⁺ (30), 195 [M-N^(i)Pr₂—H^(i)Pr]⁺ (100),181 [M-N^(i)Pr₂—^(i)Pr-Me]⁺ (40). FIG. 17 GC Chromatogram of reactionmixture after chlorination of (H₃Si)₂N(SiH₂(N^(i)Pr₂)).

Example 16. Chlorination of (H₃Si)₂N(SiH₂(NEt₂

Preparation followed the procedure shown in Example 7.2. New compounds,(H₃Si)(H₂SiCl)N(SiH₂(NEt₂)), (H₂SiCl)₂N(SiH₂(NEt₂)) and(H₂SiCl)N(SiH₂(NEt₂))₂, are synthesized herein as a result ofapplication of the disclosed method for selective chlorination ofaminosilanes with Ph₃CCl and applying a catalyst.

Reactions started with mixing (H₃Si)₂N(SiH₂(NEt₂)) (1.98 g, 11.1 mmol),Ph₃CCl (2.16 g, 7.75 mmol), Pd/C (0.42 g, 10% Pd, 0.4 mmol), toluene (7g). CG of the filtered reaction mixture is (H₃Si)₃N (0.13%),(H₃Si)₂N(SiH₂Cl) (3.83%), toluene (82.02%), (H₃Si)₂N(SiH₂(NEt₂))(7.87%). (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)) (1.92%), (H₂SiCl)₂N(SiH₂(NEt₂))(0.17%). (H₃Si)N(SiH₂(NEt₂))₂ (0.41%). (H₂SiCl)N(SiH₂(NEt₂))₂ (0.19%)and Ph₃CH (3.05%). The yield of (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)) is 21% from(H₃Si)₂N(SiH₂(NEt₂)) assuming that chlorination proceeds by equation:3(H₃Si)₂N(SiH₂(NEt₂))+2Ph₃CCl=(H₃Si)(H₂SiCl)N(SiH₂(NEt₂))+(H₃Si)₂N(SiH₂Cl)+(H₃Si)N(SiH₂(NEt₂))₂+Ph₃CH.

i. Compound (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)). Observed in mass spectrumpatterns of molecular ion assigned to (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)) aresimilar to calculated ones for [C₄H₁₇N₂Si₃Cl]⁺ (m/z=212). MS(H₃Si)(H₂SiCl)N(SiH₂(NEt₂)): 212 [M]⁺ overlapped with 211 [M-H]⁺ (15%),197 [M-Me]⁺ (100%), 183 [M-Et]⁺ (8%), 167 [M-CH₄-Et]⁺ (10) and 140[M-NEt₂]⁺ (30).

ii. Compound (H₂SiCl)₂N(SiH₂(NEt₂)). Observed in mass spectrum patternsof molecular ion assigned to (H₂SiCl)₂N(SiH₂(NEt₂)) are similar tocalculated ones for [C₄H₁₇N₂Si₃Cl]⁺ (m/z=246). MS(H₂SiCl)₂N(SiH₂(NEt₂)): 246 [M]⁺ overlapped with 245 [M-H]⁺ (11%), 231[M-Me]⁺ (100%), 217 [M-Et]⁺ (10), 208 [M-H—HCl]⁺ (15), 203 [M-NEt]⁺(15), 174 [M-NEt₂]⁺ (35) and 134 [M-SiH₃Cl—C₃H₈—H₂]⁺ (50).

iii. Compound (H₂SiCl)N(SiH₂(NEt₂))₂. Observed in mass spectrum patternsof molecular ion assigned to (H₂SiCl)N(SiH₂(NEt₂))₂ are similar tocalculated ones for [C₄H₁₇N₂Si₃Cl]⁺ (m/z=283). MS(H₂SiCl)N(SiH₂(NEt₂))₂: 283 [M]⁺ overlapped with 282 [M-H]⁺ (10%), 211[M-NEt₂]⁺ (100), 197 [M-2NEt]⁺ overlapped with 195 [M-CH₄-NEt₂]⁺ (35%),181 [M-HEt-NEt₂]⁺ (30), 167 [M-Me-Et-NEt₂]⁺ (30) and 140 [M-NC₄H₉-NEt₂]⁺(20).

It will be understood that many additional changes in the details,materials, steps, and arrangement of parts, which have been hereindescribed and illustrated in order to explain the nature of theinvention, may be made by those skilled in the art within the principleand scope of the invention as expressed in the appended claims. Thus,the present invention is not intended to be limited to the specificembodiments in the examples given above and/or the attached drawings.

While embodiments of this invention have been shown and described,modifications thereof may be made by one skilled in the art withoutdeparting from the spirit or teaching of this invention. The embodimentsdescribed herein are exemplary only and not limiting. Many variationsand modifications of the composition and method are possible and withinthe scope of the invention. Accordingly the scope of protection is notlimited to the embodiments described herein, but is only limited by theclaims which follow, the scope of which shall include all equivalents ofthe subject matter of the claims.

What is claimed is:
 1. A method for producing halosilazane, the methodcomprising halogenating a hydrosilazane with a trityl halidehalogenating agent to produce the halosilazane, the halosilazane havinga formula(SiH_(a)(NR₂)_(b)X_(c))_((n+2))N_(n)(SiH_((2−d))X_(d))_((n−1)), whereineach a, b, c is independently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1;wherein X is selected from a halogen atom selected from F, Cl, Br or I;each R is selected from H, a C₁-C₆ linear or branched, saturated orunsaturated hydrocarbyl group, or a silyl group [SiR′₃]; further whereineach R′ of the [SiR′₃] is independently selected from H, a halogen atomselected from F, Cl, Br or I, a C₁-C₄ saturated or unsaturatedhydrocarbyl group, a C₁-C₄ saturated or unsaturated alkoxy group, or anamino group [—NR¹R²] with each R¹ and R² being further selected from Hor a C₁-C₆ linear or branched, saturated or unsaturated hydrocarbylgroup, provided that when c=0, d≠0; or d=0, c≠0, and wherein thehalogenating step includes the steps of forming a mixture comprising thehydrosilazane, the halogenating agent; adding a catalyst into themixture; and separating the formed halosilazane from the mixture,wherein the halosilazane is produced by selective halogenation of thehydrosilazane that has a general formula(SiH_(a)(NR₂)_(b))_((n+2))N_(n)(SiH₂)_((n−1)), wherein each a, b, c isindependently 0 to 3; a+b+c=3; d is 0 to 2 and n≥1; wherein X isselected from a halogen atom selected from F, Cl, Br or I; each R isselected from H, a C₁-C₆ linear or branched, saturated or unsaturatedhydrocarbyl group, or a silyl group [SiR′₃]; further wherein each R′ ofthe [SiR′₃] is independently selected from H, a halogen atom selectedfrom F, Cl, Br or I, a C₁-C₄ saturated or unsaturated hydrocarbyl group,a C₁-C₄ saturated or unsaturated alkoxy group, or an amino group[—NR¹R²] with each R¹ and R² being further selected from H or a C₁-C₆linear or branched, saturated or unsaturated hydrocarbyl group, whereina selectivity of halogenation of the hydrosilazane ranges fromapproximately 30% to approximately 100%.
 2. The method of claim 1,wherein the mixture includes a solvent.
 3. The method of claim 1,wherein the halogenating the hydrosilazane with the halogenating agentis in a liquid phase.
 4. The method of claim 1, wherein the molar ratioof the halogenating agent relative to the hydrosilazane is from 1 to100% for selective synthesis of the halosilazane.
 5. The method of claim1, wherein the trityl halide is selected from Ph₃CF, Ph₃CCl, Ph₃CBr orPh₃Cl.
 6. The method of claim 1, wherein the trityl halide is Ph₃CCI. 7.The method of claim 2, wherein the solvent is selected from methylenechloride, chloroform, chloroethanes, chlorobenzenes, toluene, xylene,mesitylene, anisole, pentane, hexane, heptane, octane or mixturesthereof.
 8. The method of claim 1, wherein the catalyst is a homogeneouscatalyst selected from BPh₃ or B(SiMe₃)₃.
 9. The method of claim 1,wherein the catalyst is a heterogeneous catalyst selected from Ru, Pt orPd in elemental form or deposited on an inert support surface.
 10. Themethod of claim 1, wherein the halogenating the hydrosilazane in thepresence of the catalyst with the halogenating agent is in a liquidphase.
 11. The method of claim 1, wherein the temperature of thehalogenation ranges from approximately 20° C. to approximately 200° C.12. The method of claim 1, wherein the pressure of the halogenation isfrom approximately 0 psig to approximately 50 psig.
 13. The method ofclaim 1, wherein a yield of halogenation of the hydrosilazane rangesfrom approximately 30% to approximately 90%.
 14. The method of claim 1,wherein a selectivity of halogenation of the hydrosilazane is up toapproximately 97%.
 15. The method of claim 1, wherein each R is H. 16.The method of claim 15, wherein the halosilazanes precursors arecarbon-free halosilazanes precursors have a formula(Si_(a)H_(2a+1))_(n+2−c)(Si_(a)H_(2a+1−m)X_(m))_(c)N_(n)(SiH₂)_((n−1−d))(SiH_(2−b)X_(b))_(d),where X is selected from a halogen atom selected from F, Cl, Br or I; a,n≥1, 0<m<2a+1 and b=0-2, 0<c<n+2 and 0≤d<n−1.
 17. The method of claim 1,wherein the halosilazane is selected from (H₃Si)₂N(SiH₂Cl),(H₃Si)N(SiH₂Br)₂, (H₃Si)₂N(SiH₂I), (H₃Si)N(SiH₂Cl)₂,(H₃Si)(H₂SiCl)N(SiH₂(N^(i)Pr₂)), (H₃Si)(H₂SiBr)N(SiH₂(NiPr₂)),(H₃Si)(H₂SiI)N(SiH₂(N^(i)Pr₂)), (H₃Si)(H₂SiCl)N(SiH₂(NEt₂)),(H₃Si)(H₂SiBr)N(SiH₂(NEt₂)), (H₃Si)(H₂SiI)N(SiH₂(NEt₂)),(H₂SiCl)₂N(SiH₂(N^(i)Pr₂)), (H₃SiCl)N(SiH₂(N^(i)Pr₂))₂,(H₂SiCl)N(SiH₂(NEt₂))₂, (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Cl),(H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂Br) or (H₃Si)₂N(SiH₂)N(SiH₃)(SiH₂I).